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Sample records for photoelectron spectra xps

  1. Photoelectron Spectra

    ERIC Educational Resources Information Center

    Bock, Hans; Mollere, Phillip D.

    1974-01-01

    Presents an experimental approach to teaching molecular orbital models. Suggests utilizing photoelectron spectroscopy and molecular orbital theory as complementary approaches to teaching the qualitative concepts basic to molecular orbital theory. (SLH)

  2. Negative Ion Photoelectron Spectra of Halomethyl Anions

    NASA Astrophysics Data System (ADS)

    Vogelhuber, Kristen M.; Wren, Scott W.; McCoy, Anne B.; Ervin, Kent M.; Lineberger, W. Carl

    2009-06-01

    Halomethyl anions undergo a significant geometry change upon electron photodetachment, resulting in multiple extended vibrational progressions in the photoelectron spectra. The normal mode analysis that successfully models photoelectron spectra when geometry changes are modest is unable to reproduce the experimental data using physically reasonable parameters. A three-dimensional anharmonic coupled-mode analysis was employed to accurately reproduce the observed vibrational structure. We present the 364 nm negative ion photoelectron spectra of the halomethyl anions CHX_2^- and CDX_2^- (X = Cl, Br, I) and report electron affinities, vibrational frequencies, and geometries.

  3. Quantitative analysis of satellite structures in XPS spectra of gold and silver

    NASA Astrophysics Data System (ADS)

    Pauly, N.; Yubero, F.; Tougaard, S.

    2016-10-01

    Identification of specific chemical states and local electronic environments at surfaces by X-ray photoelectron spectroscopy (XPS) is often difficult because it is not straightforward to quantitatively interpret the shape and intensity of shake-up structures that originate from the photoexcitation process. Indeed the shape and intensity of measured XPS structures are strongly affected by both extrinsic excitations due to electron transport out of the surface and intrinsic excitations induced by the sudden creation of the static core hole. These processes must be taken into account to quantitatively extract, from experimental XPS, the primary excitation spectrum of the considered transition which includes all effects that are part of the initial photo-excitation process, i.e. lifetime broadening, spin-orbit coupling, and multiplet splitting. It was previously shown [N. Pauly, S. Tougaard, F. Yubero, Surf. Sci. 620 (2014) 17] that both extrinsic and intrinsic excitations could be included in an effective energy-differential inelastic electron scattering cross section for XPS which is then convoluted with the primary excitation spectrum to model the full XPS spectrum. This method can thus be applied to determine the primary excitation spectrum from any XPS spectrum. We use this approach in the present paper to determine the Au 4f and Ag 3d photoemission spectra from pure metals. We observe that characteristic energy loss features of the XPS spectra are not only due to photoelectron energy losses. We thus prove the existence of a double shake-up process characterized by a 4d → 5s/5p transition for Ag and a 5d → 6s/6p transition for Au. We finally accurately quantify the energy position and intensity of these shake-up peaks.

  4. Quantum optimal control of photoelectron spectra and angular distributions

    NASA Astrophysics Data System (ADS)

    Goetz, R. Esteban; Karamatskou, Antonia; Santra, Robin; Koch, Christiane P.

    2016-01-01

    Photoelectron spectra and photoelectron angular distributions obtained in photoionization reveal important information on, e.g., charge transfer or hole coherence in the parent ion. Here we show that optimal control of the underlying quantum dynamics can be used to enhance desired features in the photoelectron spectra and angular distributions. To this end, we combine Krotov's method for optimal control theory with the time-dependent configuration interaction singles formalism and a splitting approach to calculate photoelectron spectra and angular distributions. The optimization target can account for specific desired properties in the photoelectron angular distribution alone, in the photoelectron spectrum, or in both. We demonstrate the method for hydrogen and then apply it to argon under strong XUV radiation, maximizing the difference of emission into the upper and lower hemispheres, in order to realize directed electron emission in the XUV regime.

  5. [Surface and interface analysis of PTCDA/ITO using X-ray photoelectron spectroscopy (XPS)].

    PubMed

    Ou, Gu-ping; Song, Zhen; Gui, Wen-ming; Zhang, Fu-jia

    2006-04-01

    X-ray photoelectron spectroscopy (XPS) of surface and interface of PTCDA/ITO in PTCDA/p-Si organic-on-inorganic photoelectric detector was investigated. From C1s fine spectrum we found that the binding energy of C atoms in perylene rings was 284.6 eV; and the binding energy of C atoms in acid radical was 288.7 eV; moreover, some C atoms were oxidized by O atoms from ITO. The binding energy of O atoms in C=O bonds and C-O-C bonds was 531.5 and 533.4 eV, respectively. At the interface, the peak of high binding energy in C1s spectrum disappeared, and the main peak shifted toward lower binding energy.

  6. Repair and Utilization of the Kratos XSAM 800 X-Ray Photoelectron Spectrometer (XPS)

    NASA Technical Reports Server (NTRS)

    Hampton, Michael D.

    2002-01-01

    The objectives for this summer faculty fellowship were first to repair the Kratos XSAM 800 X-ray Photoelectron Spectrometer (XPS) and then to utilize the instrument to participate in ongoing research projects at KSC and in the researcher's own laboratory at UCF. The first 6 weeks were used in repairing the instrument. Working both alone and with the Kratos service engineer, a number of hardware problems, largely associated with the sample stage control system, were corrected. Defective parts were identified and fixed in the computer driver boards, the stage power supply, and the driver interface. The power supply was completely replaced. After four weeks of work, the instrument was functional. This occurred on a Wednesday. The following Friday the instrument had to be completely shut down because the power to the O & C Building was to be turned off. The instrument was properly secured. On Monday, the instrument was powered up and the original problems returned. After another 2 weeks of work, a software problem was identified. This problem caused the computer to use a defective port for the sample stage control. It was circumvented by rewriting the startup routine. The final 3 weeks of the fellowship were spent using the XPS to analyze samples being studied in the Langley materials project (Martha Williams) and a catalyst project (Dr. Orlando Melendez). During this time, several sample analysis requests from other groups at KSC also came in and those samples were run as well. The summer faculty fellowship also allowed many contacts to be made. After meeting with the sensors group, two projects were identified for collaboration and white papers are being prepared. One project aims to develop small, very sensitive hydrogen detectors and the other to develop a broad area, easily monitored, zero power consumption hydrogen detector. In addition to the work mentioned above, the XPS was utilized in a study underway in Dr. Hampton's laboratory at UCF.

  7. The Interpretation of XPS Spectra: Insights Into Materials Properties

    SciTech Connect

    Bagus, Paul S.; Ilton, Eugene S.; Nelin, Constance J.

    2013-06-01

    We review basic and advanced concepts needed for the correct analysis of XPS features. We place these concepts on rigorous foundations and explore their physical and chemical meanings without stressing the derivation of the mathematical formulations, which can be found in the cited literature. The significance and value of combining theory and experiment is demonstrated by discussions of the physical and chemical origins of the main and satellite XPS features for a variety of molecular and condensed phase materials.

  8. Interatomic scattering in energy dependent photoelectron spectra of Ar clusters

    SciTech Connect

    Patanen, M.; Benkoula, S.; Nicolas, C.; Goel, A.; Antonsson, E.; Neville, J. J.; Miron, C.

    2015-09-28

    Soft X-ray photoelectron spectra of Ar 2p levels of atomic argon and argon clusters are recorded over an extended range of photon energies. The Ar 2p intensity ratios between atomic argon and clusters’ surface and bulk components reveal oscillations similar to photoelectron extended X-ray absorption fine structure signal (PEXAFS). We demonstrate here that this technique allows us to analyze separately the PEXAFS signals from surface and bulk sites of free-standing, neutral clusters, revealing a bond contraction at the surface.

  9. A poly-epoxy surface explored by Hartree-Fock ΔSCF simulations of C1s XPS spectra

    NASA Astrophysics Data System (ADS)

    Gavrielides, A.; Duguet, T.; Esvan, J.; Lacaze-Dufaure, C.; Bagus, P. S.

    2016-08-01

    Whereas poly-epoxy polymers represent a class of materials with a wide range of applications, the structural disorder makes them difficult to model. In the present work, we use good experimental model samples in the sense that they are pure, fully polymerized, flat and smooth, defect-free, and suitable for ultrahigh vacuum x-ray photoelectron spectroscopy, XPS, experiments. In parallel, we perform Hartree-Fock, HF, calculations of the binding energies, BEs, of the C1s electrons in a model molecule composed of the two constituents of the poly-epoxy sample. These C1s BEs were determined using the HF ΔSCF method, which is known to yield accurate values, especially for the shifts of the BEs, ΔBEs. We demonstrate the benefits of combining rigorous theory with careful XPS measurements in order to obtain correct assignments of the C1s XPS spectra of the polymer sample. Both the relative binding energies—by the ΔSCF method—and relative intensities—in the sudden approximation, SA, are calculated. It results in an excellent match with the experimental spectra. We are able to identify 9 different chemical environments under the C1s peak, where an exclusively experimental work would have found only 3 contributions. In addition, we observe that some contributions are localized at discrete binding energies, whereas others allow a much wider range because of the variation of their second neighbor bound polarization. Therefore, HF-ΔSCF simulations significantly increase the spectral resolution of XPS and thus offer a new avenue for the exploration of the surface of polymers.

  10. A poly-epoxy surface explored by Hartree-Fock ΔSCF simulations of C1s XPS spectra.

    PubMed

    Gavrielides, A; Duguet, T; Esvan, J; Lacaze-Dufaure, C; Bagus, P S

    2016-08-21

    Whereas poly-epoxy polymers represent a class of materials with a wide range of applications, the structural disorder makes them difficult to model. In the present work, we use good experimental model samples in the sense that they are pure, fully polymerized, flat and smooth, defect-free, and suitable for ultrahigh vacuum x-ray photoelectron spectroscopy, XPS, experiments. In parallel, we perform Hartree-Fock, HF, calculations of the binding energies, BEs, of the C1s electrons in a model molecule composed of the two constituents of the poly-epoxy sample. These C1s BEs were determined using the HF ΔSCF method, which is known to yield accurate values, especially for the shifts of the BEs, ΔBEs. We demonstrate the benefits of combining rigorous theory with careful XPS measurements in order to obtain correct assignments of the C1s XPS spectra of the polymer sample. Both the relative binding energies-by the ΔSCF method-and relative intensities-in the sudden approximation, SA, are calculated. It results in an excellent match with the experimental spectra. We are able to identify 9 different chemical environments under the C1s peak, where an exclusively experimental work would have found only 3 contributions. In addition, we observe that some contributions are localized at discrete binding energies, whereas others allow a much wider range because of the variation of their second neighbor bound polarization. Therefore, HF-ΔSCF simulations significantly increase the spectral resolution of XPS and thus offer a new avenue for the exploration of the surface of polymers. PMID:27544119

  11. Spectroscopic studies of superconductors. Part B: Tunneling, photoelectron, and other spectra

    SciTech Connect

    Bozovic, I.; Marel, D. van der

    1996-12-31

    Part B is divided into the following sections: (1) tunneling, photoelectron, and other spectra; (2) tunneling spectra: theoretical studies; (3) photoelectron spectra; and (4) other spectra (XAFS, RBS, ESR, Moessbauer, thermoreflectance, etc.). Separate abstracts were prepared for most papers in this volume.

  12. On the analysis of photo-electron spectra

    SciTech Connect

    Gao, C.-Z.; Dinh, P.M.; Reinhard, P.-G.; Suraud, E.

    2015-09-15

    We analyze Photo-Electron Spectra (PES) for a variety of excitation mechanisms from a simple mono-frequency laser pulse to involved combination of pulses as used, e.g., in attosecond experiments. In the case of simple pulses, the peaks in PES reflect the occupied single-particle levels in combination with the given laser frequency. This usual, simple rule may badly fail in the case of excitation pulses with mixed frequencies and if resonant modes of the system are significantly excited. We thus develop an extension of the usual rule to cover all possible excitation scenarios, including mixed frequencies in the attosecond regime. We find that the spectral distributions of dipole, monopole and quadrupole power for the given excitation taken together and properly shifted by the single-particle energies provide a pertinent picture of the PES in all situations. This leads to the derivation of a generalized relation allowing to understand photo-electron yields even in complex experimental setups.

  13. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    SciTech Connect

    Embong, Zaidi; Johar, Saffuwan; Tajudin, Saiful Azhar Ahmad; Sahdan, Mohd Zainizan

    2015-04-29

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si{sup 2+} and Al{sup 2+} cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  14. Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

    NASA Astrophysics Data System (ADS)

    Embong, Zaidi; Johar, Saffuwan; Tajudin, Saiful Azhar Ahmad; Sahdan, Mohd Zainizan

    2015-04-01

    Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangau soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si2+ and Al2+ cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.

  15. X-ray photoelectron spectroscopy (XPS) investigation of the surface film on magnesium powders.

    PubMed

    Burke, Paul J; Bayindir, Zeynel; Kipouros, Georges J

    2012-05-01

    Magnesium (Mg) and its alloys are attractive for use in automotive and aerospace applications because of their low density and good mechanical properties. However, difficulty in forming magnesium and the limited number of available commercial alloys limit their use. Powder metallurgy may be a suitable solution for forming near-net-shape parts. However, sintering pure magnesium presents difficulties due to surface film that forms on the magnesium powder particles. The present work investigates the composition of the surface film that forms on the surface of pure magnesium powders exposed to atmospheric conditions and on pure magnesium powders after compaction under uniaxial pressing at a pressure of 500 MPa and sintering under argon at 600 °C for 40 minutes. Initially, focused ion beam microscopy was utilized to determine the thickness of the surface layer of the magnesium powder and found it to be ~10 nm. The X-ray photoelectron analysis of the green magnesium sample prior to sintering confirmed the presence of MgO, MgCO(3)·3H(2)O, and Mg(OH)(2) in the surface layer of the powder with a core of pure magnesium. The outer portion of the surface layer was found to contain MgCO(3)·3H(2)O and Mg(OH)(2), while the inner portion of the layer is primarily MgO. After sintering, the MgCO(3)·3H(2)O was found to be almost completely absent, and the amount of Mg(OH)(2) was also decreased significantly. This is postulated to occur by decomposition of the compounds to MgO and gases during the high temperature of sintering. An increase in the MgO content after sintering supports this theory.

  16. Application of maximum-entropy spectral estimation to deconvolution of XPS data. [X-ray Photoelectron Spectroscopy

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Klein, J. D.; Barton, J. J.; Grunthaner, F. J.

    1981-01-01

    A comparison is made between maximum-entropy spectral estimation and traditional methods of deconvolution used in electron spectroscopy. The maximum-entropy method is found to have higher resolution-enhancement capabilities and, if the broadening function is known, can be used with no adjustable parameters with a high degree of reliability. The method and its use in practice are briefly described, and a criterion is given for choosing the optimal order for the prediction filter based on the prediction-error power sequence. The method is demonstrated on a test case and applied to X-ray photoelectron spectra.

  17. Understanding Chemical versus Electrostatic Shifts in X-ray Photoelectron Spectra of Organic Self-Assembled Monolayers

    PubMed Central

    2016-01-01

    The focus of the present article is on understanding the insight that X-ray photoelectron spectroscopy (XPS) measurements can provide when studying self-assembled monolayers. Comparing density functional theory calculations to experimental data on deliberately chosen model systems, we show that both the chemical environment and electrostatic effects arising from a superposition of molecular dipoles influence the measured core-level binding energies to a significant degree. The crucial role of the often overlooked electrostatic effects in polar self-assembled monolayers (SAMs) is unambiguously demonstrated by changing the dipole density through varying the SAM coverage. As a consequence of this effect, care has to be taken when extracting chemical information from the XP spectra of ordered organic adsorbate layers. Our results, furthermore, imply that XPS is a powerful tool for probing local variations in the electrostatic energy in nanoscopic systems, especially in SAMs. PMID:26937264

  18. Theoretical characterization of X-ray absorption, emission, and photoelectron spectra of nitrogen doped along graphene edges.

    PubMed

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Oshima, Masaharu; Kakimoto, Masa-aki; Terakura, Kiyoyuki

    2013-01-24

    K-edge X-ray absorption (XAS), emission (XES), and photoelectron (XPS) spectra of nitrogen doped along graphene edges are systematically investigated by using first-principles methods. In this study we considered pyridinium-like, pyridine-like, cyanide-like, and amine-like nitrogens at armchair and zigzag edges and pyrrole-like nitrogen at armchair edge as well as graphite-like nitrogen at graphene interior site. Our results indicate that nitrogen configuration and its location (armchair or zigzag edge) in nitrogen-doped graphene can be identified via the spectral analysis. Furthermore, some controversial spectral features observed in experiment for N-doped graphene-like materials are unambiguously assigned. The present analysis gives an explanation to the reason why the peak assignment is usually made differently between XPS and XAS.

  19. An XPS study of the stability of Fomblin Z25 on the native oxide of aluminum. [x ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

    1991-01-01

    Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum and sapphire surfaces, and their behavior at different temperatures was studied using x ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). It was found that the interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. Our conclusion is that the native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At high temperatures (150 C) degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formulation of a debris layer.

  20. Assignment of benzodiazepine UV absorption spectra by the use of photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Khvostenko, O. G.; Tzeplin, E. E.; Lomakin, G. S.

    2002-04-01

    Correlations between singlet transition energies and energy gaps of corresponding pairs of occupied and unoccupied molecular orbitals were revealed in a series of benzodiazepines. The occupied orbital energies were taken from the photoelectron spectra of the compound investigated, the unoccupied ones were obtained from MNDO/d calculations, and the singlet energies were taken from the UV absorption spectra. The correspondence of the singlet transitions to certain molecular orbitals was established using MNDO/d calculations and comparing between UV and photoelectron spectra. It has been concluded that photoelectron spectroscopy can be applied for interpretation of UV absorption spectra of various compounds on the basis of similar correlations.

  1. Photoelectron spectra with QPROP and t-SURFF

    NASA Astrophysics Data System (ADS)

    Mosert, Volker; Bauer, Dieter

    2016-10-01

    Calculating strong-field, momentum-resolved photoelectron spectra (PES) from numerical solutions of the time-dependent Schrödinger equation (TDSE) is a very demanding task due to the large spatial excursions and drifts of electrons in intense laser fields. The time-dependent surface flux (t-SURFF) method for the calculation of PES [Tao and Scrinzi (2012)] allows to keep the numerical grid much smaller than the space over which the wavefunction would be spread at the end of the laser pulse. We present an implementation of the t-SURFF method in the well established TDSE-solver QPROP [Bauer and Koval (2006)]. QPROP efficiently propagates wavefunctions for single-active electron systems with spherically symmetric binding potentials in classical, linearly (along z) or elliptically (in the xy-plane) polarized laser fields in dipole approximation. Its combination with t-SURFF makes the simulation of PES feasible in cases where it is just too expensive to keep the entire wavefunction on the numerical grid, e.g., in the long-wavelength or long-pulse regime. Catalogue identifier: ADXB_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADXB_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License, version 3 No. of lines in distributed program, including test data, etc.: 12458 No. of bytes in distributed program, including test data, etc.: 86258 Distribution format: at.gz Programming language: C++. Computer: x86_64. Operating system: Linux. RAM: The memory requirements for calculating PES are determined by the maximum ℓ in the spherical harmonics expansion of the wave function and the number of momentum (or energy) values for which the PES are to be calculated. The example with the largest memory demand (large-clubs) uses approximately 6GB of RAM. The size of the numerical representation of a wavefunction during propagation is modest for the examples included (53 MB for the large

  2. Symmetry adapted cluster-configuration interaction calculation of the photoelectron spectra of famous biological active steroids

    NASA Astrophysics Data System (ADS)

    Abyar, Fatemeh; Farrokhpour, Hossein

    2014-11-01

    The photoelectron spectra of some famous steroids, important in biology, were calculated in the gas phase. The selected steroids were 5α-androstane-3,11,17-trione, 4-androstane-3,11,17-trione, cortisol, cortisone, corticosterone, dexamethasone, estradiol and cholesterol. The calculations were performed employing symmetry-adapted cluster/configuration interaction (SAC-CI) method using the 6-311++G(2df,pd) basis set. The population ratios of conformers of each steroid were calculated and used for simulating the photoelectron spectrum of steroid. It was found that more than one conformer contribute to the photoelectron spectra of some steroids. To confirm the calculated photoelectron spectra, they compared with their corresponding experimental spectra. There were no experimental gas phase Hesbnd I photoelectron spectra for some of the steroids of this work in the literature and their calculated spectra can show a part of intrinsic characteristics of this molecules in the gas phase. The canonical molecular orbitals involved in the ionization of each steroid were calculated at the HF/6-311++g(d,p) level of theory. The spectral bands of each steroid were assigned by natural bonding orbital (NBO) calculations. Knowing the electronic structures of steroids helps us to understand their biological activities and find which sites of steroid become active when a modification is performing under a biological pathway.

  3. Self-consistent modelling of X-ray photoelectron spectra from air-exposed polycrystalline TiN thin films

    NASA Astrophysics Data System (ADS)

    Greczynski, G.; Hultman, L.

    2016-11-01

    We present first self-consistent modelling of x-ray photoelectron spectroscopy (XPS) Ti 2p, N 1s, O 1s, and C 1s core level spectra with a cross-peak quantitative agreement for a series of TiN thin films grown by dc magnetron sputtering and oxidized to different extent by varying the venting temperature Tv of the vacuum chamber before removing the deposited samples. So-obtained film series constitute a model case for XPS application studies, where certain degree of atmosphere exposure during sample transfer to the XPS instrument is unavoidable. The challenge is to extract information about surface chemistry without invoking destructive pre-cleaning with noble gas ions. All TiN surfaces are thus analyzed in the as-received state by XPS using monochromatic Al Kα radiation (hν = 1486.6 eV). Details of line shapes and relative peak areas obtained from deconvolution of the reference Ti 2p and N 1 s spectra representative of a native TiN surface serve as an input to model complex core level signals from air-exposed surfaces, where contributions from oxides and oxynitrides make the task very challenging considering the influence of the whole deposition process at hand. The essential part of the presented approach is that the deconvolution process is not only guided by the comparison to the reference binding energy values that often show large spread, but in order to increase reliability of the extracted chemical information the requirement for both qualitative and quantitative self-consistency between component peaks belonging to the same chemical species is imposed across all core-level spectra (including often neglected O 1s and C 1s signals). The relative ratios between contributions from different chemical species vary as a function of Tv presenting a self-consistency check for our model. We propose that the cross-peak self-consistency should be a prerequisite for reliable XPS peak modelling as it enhances credibility of obtained chemical information, while relying

  4. Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra

    PubMed Central

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-01-01

    Time-resolved photoelectron spectroscopy is commonly employed with the intention to monitor electronic excited-state dynamics occurring in a neutral molecule. With the help of theory, we show that when excited-state processes occur on similar time scales the different relaxation pathways are completely obscured in the total photoionization signal recorded in the experiment. Using non-adiabatic molecular dynamics and Dyson norms, we calculate the photoionization signal of cytosine and disentangle the transient contributions originating from the different deactivation pathways of its tautomers. In the simulations, the total signal from the relevant keto and enol tautomers can be decomposed into contributions either from the neutral electronic state populations or from the distinct mechanistic pathways across the multiple potential surfaces. The lifetimes corresponding to these contributions cannot be extracted from the experiment, thereby illustrating that new experimental setups are necessary to unravel the intricate non-adiabatic pathways occurring in polyatomic molecules after irradiation by light. PMID:27762396

  5. Vibrationally resolved high-resolution NEXAFS and XPS spectra of phenanthrene and coronene

    SciTech Connect

    Fronzoni, Giovanna; Baseggio, Oscar; Stener, Mauro; Hua, Weijie; Tian, Guangjun; Luo, Yi; Apicella, Barbara; Alfé, Michela; Simone, Monica de; Kivimäki, Antti; Coreno, Marcello

    2014-07-28

    We performed a combined experimental and theoretical study of the C1s Near-Edge X-ray Absorption Fine-Structure (NEXAFS) spectroscopy and X-ray Photoelectron Spectroscopy in the gas phase of two polycyclic aromatic hydrocarbons (phenanthrene and coronene), typically formed in combustion reactions. In the NEXAFS of both molecules, a double-peak structure appears in the C1s → LUMO region, which differ by less than 1 eV in transition energies. The vibronic coupling is found to play an important role in such systems. It leads to weakening of the lower-energy peak and strengthening of the higher-energy one because the 0 − n (n > 0) vibrational progressions of the lower-energy peak appear in nearly the same region of the higher-energy peak. Vibrationally resolved theoretical spectra computed within the Frank-Condon (FC) approximation and linear coupling model agree well with the high-resolution experimental results. We find that FC-active normal modes all correspond to in-plane vibrations.

  6. Derivation of dielectric function and inelastic mean free path from photoelectron energy-loss spectra of amorphous carbon surfaces

    NASA Astrophysics Data System (ADS)

    David, Denis; Godet, Christian

    2016-11-01

    Photoelectron Energy Loss Spectroscopy (PEELS) is a highly valuable non destructive tool in applied surface science because it gives access to both chemical composition and electronic properties of surfaces, including the near-surface dielectric function. An algorithm is proposed for real materials to make full use of experimental X-ray photoelectron spectra (XPS). To illustrate the capabilities and limitations of this algorithm, the near-surface dielectric function ε(ℏω) of a wide range of amorphous carbon (a-C) thin films is derived from energy losses measured in XPS, using a dielectric response theory which relates ε(ℏω) and the bulk plasmon (BP) loss distribution. Self-consistent separation of bulk vs surface plasmon excitations, deconvolution of multiple BP losses and evaluation of Bethe-Born sensitivity factors for bulk and surface loss distributions are crucial to obtain several material parameters: (1) energy loss function for BP excitation, (2) dielectric function of the near-surface material (3-5 nm depth sensitivity), (3) inelastic mean free path, λP (E0), for plasmon excitation, (4) surface excitation parameter, (5) effective number NEFF of valence electrons participating in the plasma oscillation. This photoelectron energy loss spectra analysis has been applied to a-C and a-C:H films grown by physical and chemical methods with a wide range of (sp3/sp2 + sp3) hybridization, optical gap and average plasmon energy values. Different methods are assessed to accurately remove the photoemission peak tail at low loss energy (0-10 eV) due to many-body interactions during the photo-ionization process. The σ + π plasmon excitation represents the main energy-loss channel in a-C; as the C atom density decreases, λP (970 eV) increases from 1.22 nm to 1.6 nm, assuming a cutoff plasmon wavenumber given by a free electron model. The π-π* and σ-σ* transitions observed in the retrieved dielectric function are discussed as a function of the average (sp3/sp

  7. Electronic and geometric properties of Au nanoparticles on Highly Ordered Pyrolytic Graphite (HOPG) studied using X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM).

    PubMed

    Lopez-Salido, Ignacio; Lim, Dong Chan; Dietsche, Rainer; Bertram, Nils; Kim, Young Dok

    2006-01-26

    Au nanoparticles grown on mildly sputtered Highly Ordered Pyrolytic Graphite (HOPG) surfaces were studied using Scanning Tunneling Microscopy (STM) and X-ray Photoelectron Spectroscopy (XPS). The results were compared with those of Ag nanoparticles on the same substrate. By varying the defect densities of HOPG and the Au coverages, one can create Au nanoparticles in various sizes. At high Au coverages, the structures of the Au films significantly deviate from the ideal truncated octahedral form: the existence of many steps between different Au atomic layers can be observed, most likely due to a high activation barrier of the diffusion of Au atoms across the step edges. This implies that the particle growth at room temperature is strongly limited by kinetic factors. Hexagonal shapes of Au structures could be identified, indicating preferential growth of Au nanostructures along the (111) direction normal to the surface. In the case of Au, XPS studies reveal a weaker core level shift with decreasing particle size compared to the 3d level in similarly sized Ag particles. Also taking into account the Auger analysis of the Ag particles, the core level shifts of the metal nanoparticles on HOPG can be understood in terms of the metal/substrate charge transfer. Ag is (partially) positively charged, whereas Au negatively charged on HOPG. It is demonstrated that XPS can be a useful tool to study metal-support interactions, which plays an important role for heterogeneous catalysis, for example.

  8. Photoelectron spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil

    NASA Astrophysics Data System (ADS)

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-02-01

    Ground- and excited-state UV photoelectron spectra of thiouracils (2-thiouracil, 4-thiouracil, and 2,4-dithiouracil) have been simulated using multireference configuration interaction calculations and Dyson norms as a measure for the photoionization intensity. Except for a constant shift, the calculated spectrum of 2-thiouracil agrees very well with experiment, while no experimental spectra are available for the two other compounds. For all three molecules, the photoelectron spectra show distinct bands due to ionization of the sulphur and oxygen lone pairs and the pyrimidine π system. The excited-state photoelectron spectra of 2-thiouracil show bands at much lower energies than in the ground state spectrum, allowing to monitor the excited-state population in time-resolved UV photoelectron spectroscopy experiments. However, the results also reveal that single-photon ionization probe schemes alone will not allow monitoring all photodynamic processes existing in 2-thiouracil. Especially, due to overlapping bands of singlet and triplet states the clear observation of intersystem crossing will be hampered.

  9. Photoelectron spectra of dihalomethyl anions: Testing the limits of normal mode analysis

    NASA Astrophysics Data System (ADS)

    Vogelhuber, Kristen M.; Wren, Scott W.; McCoy, Anne B.; Ervin, Kent M.; Lineberger, W. Carl

    2011-05-01

    We report the 364-nm negative ion photoelectron spectra of CHX2- and CDX2-, where X = Cl, Br, and I. The pyramidal dihalomethyl anions undergo a large geometry change upon electron photodetachment to become nearly planar, resulting in multiple extended vibrational progressions in the photoelectron spectra. The normal mode analysis that successfully models photoelectron spectra when geometry changes are modest is unable to reproduce qualitatively the experimental data using physically reasonable parameters. Specifically, the harmonic normal mode analysis using Cartesian displacement coordinates results in much more C-H stretch excitation than is observed, leading to a simulated photoelectron spectrum that is much broader than that which is seen experimentally. A (2 + 1)-dimensional anharmonic coupled-mode analysis much better reproduces the observed vibrational structure. We obtain an estimate of the adiabatic electron affinity of each dihalomethyl radical studied. The electron affinity of CHCl2 and CDCl2 is 1.3(2) eV, of CHBr2 and CDBr2 is 1.9(2) eV, and of CHI2 and CDI2 is 1.9(2) eV. Analysis of the experimental spectra illustrates the limits of the conventional normal mode approach and shows the type of analysis required for substantial geometry changes when multiple modes are active upon photodetachment.

  10. Origin of fine structure in si photoelectron spectra at silicon surfaces and interfaces.

    PubMed

    Yazyev, Oleg V; Pasquarello, Alfredo

    2006-04-21

    Using a first-principles approach, we investigate the origin of the fine structure in Si 2p photoelectron spectra at the Si(100)-(2 x 1) surface and at the Si(100)-SiO2 interface. Calculated and measured shifts show very good agreement for both systems. By using maximally localized Wannier functions, we clearly identify the shifts resulting from the electronegativity of second-neighbor atoms. The other shifts are then found to be proportional to the average bond-length variation around the Si atom. Hence, in combination with accurate modeling, photoelectron spectroscopy can provide a direct measure of the strain field at the atomic scale.

  11. High-resolution photoelectron spectra of the pyrimidine-type nucleobases

    SciTech Connect

    Fulfer, K. D.; Hardy, D.; Poliakoff, E. D.; Aguilar, A. A.

    2015-06-14

    High-resolution photoelectron spectra of the gas phase pyrimidine-type nucleobases, thymine, uracil, and cytosine, were collected using synchrotron radiation over the photon energy range 17 ≤ hν ≤ 150 eV. These data provide the highest resolution photoelectron spectra of thymine, uracil, and cytosine published to date. By comparing integrated regions of the energy dependent photoelectron spectra of thymine, the ionization potentials of the first four ionic states of thymine were estimated to be 8.8, 9.8, 10.3, and 10.8 eV. The thymine data also show evidence for low energy shape resonances in three of the outermost valence electronic states. Comparing the uracil spectrum with the thymine spectrum, the four outermost valence electronic states of uracil likely begin at binding energies 9.3, 9.9, 10.5, and 11.0 eV. High-resolution spectra indicate only one tautomeric form of cytosine contributes significantly to the spectrum with the four outermost valence electronic states beginning at binding energies 8.9, 9.9, 10.4, and 10.85 eV.

  12. XPS studies of structure-induced radiation effects at the Si/SiO2 interface. [X ray Photoelectron Spectroscopy

    NASA Technical Reports Server (NTRS)

    Grunthaner, F. J.; Lewis, B. F.; Zamini, N.; Maserjian, J.; Madhukar, A.

    1980-01-01

    The interfacial structures of radiation hard and soft oxides grown by dry and wet processes on silicon substrates have been examined by high-resolution X-ray photoelectron spectroscopy. It is found that the primary difference in the local atomic structure at the Si/SiO2 interface is the significantly higher concentration of strained 120 deg SiO2 bonds and SiO interfacial species in soft samples. Results of in situ radiation damage experiments using low energy electrons (0-20 eV) are reported which correlate with the presence of a strained layer of SiO2 (20 A) at the interface. The results are interpreted in terms of a structural model for hole and electron trap generation by ionizing radiation.

  13. [SIMS (secondary ion mass spectroscopy) and XPS (x-ray photoelectron spectroscopy) study of titanium implant surfaces coated with anodic titanium-oxide layer].

    PubMed

    Suba, Csongor; Velich, Norbert; Vida, György; Kovács, Lajos; Kiss, Gábor; Szabó, György

    2003-10-01

    The demands that must be satisfied by titanium implants applied in medical practice include chemical and physical durability. An anodic oxide protective layer formed on the surface of titanium implants serves for the better attainment of this aim. The composition of the passivizing layer and the changes in its thickness and binding state can be studied by method of material science, e.g. by secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). In this way a possibility arises for the material technological classification of the Ti-TiO2 layer structure and for the observation of the physical and chemical reactions that occur between the implants and the tissues in the organism. The present XPS examinations revealed that the binding state of the titanium forming the surface of the plates involve neither significant quantities of titanium oxide nor impurities. In the SIMS investigation the thickness of the titanium oxide layer was found to be 120-150 nm. Determination of the thickness of the surface, the binding state of the titanium and the exact proportions of the impurities and additives furnishes a possibility for a subsequent comparison with the surface structure of plates removed from the organism. It is important for the assessment of the practical value of the protective layer.

  14. Photoelectron spectra of thulium atoms encapsulated C82 fullerene, Tm2@C82 (III) and Tm2C2@C82 (III)

    NASA Astrophysics Data System (ADS)

    Miyazaki, Takafumi; Tokumoto, Youji; Sumii, Ryohei; Yagi, Hajime; Izumi, Noriko; Shinohara, Hisanori; Hino, Shojun

    2014-03-01

    Ultraviolet photoelectron spectra (UPS) and X-ray photoelectron spectra (XPS) of two thulium atoms and thulium-carbide cluster entrapped fullerenes, Tm2@C82 (III) and Tm2C2@C82 (III), were measured using synchrotron radiation and MgKα X-ray light sources. The UPS spectral onset energy of these endohedral fullerenes is around 0.9 eV, which is smaller than that of 1.2 eV of empty C82. The UPS of Tm2@C82 (III) and Tm2C2@C82 (III) resemble each other. Further, the UPS of Tm2@C82 (III), Y2@C82-C3v and Er2@C82-C3v are almost identical and as well as are Tm2C2@C82 (III), Y2C2@C82-C3v and Er2C2@C82-C3v. The XPS Tm4d5/2 peaks of Tm2@C82 and Tm2C2@C82 appear at higher binding energy region than that of Tm@C82, which suggests the oxidation states of Tm atoms in Tm2@C82 (III) and Tm2C2@C82 are higher than that in Tm@C82.

  15. Interpretation of x-ray photoelectron spectra of elastic amorphous carbon nitride thin films

    SciTech Connect

    Holloway, B.C.; Kraft, O.; Shuh, D.K.; Kelly, M.A.; Nix, W.D.; Pianetta, P.; Hagstroem, S.

    1999-05-01

    We report the synthesis and characterization of amorphous carbon nitride (CN{sub x}) thin films using a direct current magnetron reactive sputter system. Nanoindentation of the CN{sub x} films and amorphous carbon films deposited under similar conditions shows the CN{sub x} films are extremely elastic, that the addition of nitrogen fundamentally changes the mechanical properties of the films, and that traditional methods of calculating the hardness and Young{close_quote}s modulus may not be valid. X-ray photoelectron spectroscopy (XPS) of the N(1s) and C(1s) core levels show multiple bonding arrangements. In a new interpretation of the XPS data, the two predominant N(1s) spectral features have been identified, based on comparison to reference data in the literature, as those belonging to nitrogen in a four-bond arrangement and nitrogen in a three-bond arrangement, independent of hybridization. The formation of a fourth bond allows nitrogen to substitute for C atoms in a carbon-based graphitic system without the formation of dangling bonds or unfilled states. The relationship between nitrogen incorporation in a carbon-based ring structure and measured film properties is rationalized based on previously published models. {copyright} {ital 1999 American Institute of Physics.}

  16. Excitation of XPS spectra from nanoscaled particles by local generation of x-rays

    SciTech Connect

    Mallinson, Christopher F.; Castle, James E.

    2015-09-15

    In preliminary work, the authors have shown that use of an aluminum substrate to support a distribution of copper particles enables their characteristic photoelectrons to be observed within the Auger electron spectrum generated by an incident electron beam. This observation raises the possibility of the use of chemical shifts and the corresponding Auger parameter to identify the chemical states present on the surface of individual submicrometer particles within a mixture. In this context, the technique has an advantage in that, unlike conventional Auger electron spectroscopy, the electron beam does not dwell on the particle but on the substrate adjacent to it. Given the importance, for both medical and toxicological reasons, of the surface composition of such particles, the authors have continued to explore the potential of this development. In this contribution, the authors show that proximal excitation of x-rays is equally successful with magnesium substrates. In some regions of the x-ray photoelectron spectrum, the much larger Auger peaks generated by the electron beam can cause inconvenient clustering of Auger and photoelectron peaks. As in conventional x-ray photoelectron spectroscopy, the ability to switch between Al and Mg sources is useful in such situations. In this context, the authors have extended the studies to iron particles where the authors show that use of Al or Mg substrates, as necessary, can make a contribution to clear identification of individual components in the Fe 2p peaks. For this development in electron spectroscopy to achieve its full potential, it is necessary to optimize the beam conditions used to generate the local x-ray to give good selectivity of a given particle. Measurements made in support of this will be given. Of greater concern is a possible problem of local heating associated with x-ray generation. The authors continue to explore this problem and report some progress in minimizing heating of the particle while maintaining

  17. Photoelectron spectra and electronic structure of nitrogen analogues of boron β-diketonates

    NASA Astrophysics Data System (ADS)

    Tikhonov, Sergey A.; Vovna, Vitaliy I.; Borisenko, Aleksandr V.

    2016-07-01

    The electronic structure of the valence levels of seven nitrogen-containing boron complexes was investigated using methods of ultraviolet photoelectron spectroscopy and density functional theory. The ionization energies of π- and σ-levels were obtained from photoelectron spectra. The electronic structure of nitrogen-containing compounds was compared with the electronic structure of β-diketonates. It was shown the influence of various substituents on carbon and nitrogen atoms of six-membered ring on the electronic structure of complexes. The changes in the electronic structure after the substitution of atoms in condensed cycles have been identified. In order to compare the experimental vertical ionization energies IEi with Kohn-Sham orbital energies εi we used the analogue of Koopmans theorem and average amendment to the orbital energy of the electrons (δbari). For 26 electronic levels of seven studied complexes, the calculated values are in good accordance with experimental energy intervals between electron levels.

  18. Few-femtosecond sensitivity of ultrafast molecular dynamics with time-resolved photoelectron spectra

    NASA Astrophysics Data System (ADS)

    Champenois, Elio G.; Cryan, James P.; Larsen, Kirk; Shivaram, Niranjan H.; Belkacem, Ali

    2016-05-01

    We explore ultrafast dynamics involving non-adiabatic couplings following valence electronic excitation of small molecular systems. By measuring the time-resolved photoelectron spectra (TRPES) resulting from ionization with ultraviolet light, the excited wave packet can be tracked with state specificity. If the nuclear motion is dominated by a limited number of degrees of freedom, the TRPES also yields information about the molecular geometry. Even with limited temporal resolution, the onset times of the signal at different photoelectron energies can lead to few-femtosecond sensitivity. Applying this technique to ethylene (C2 H4) excited to the ππ* state, ultrafast motion along the twist coordinate is observed along with transient population to the π 3 s state through non-adiabatic coupling. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Divison under Contract No. DE-AC02-05CH11231.

  19. Imaging plasmonic fields near gold nanospheres in attosecond time-resolved streaked photoelectron spectra

    NASA Astrophysics Data System (ADS)

    Li, Jianxiong; Thumm, Uwe

    2016-05-01

    To study time-resolved photoemission from gold nanospheres, we introduce a quantum-mechanical approach, including the plasmonic near-field-enhancement of the streaking field at the surface of the nanosphere. We use Mie theory to calculate the plasmonically enhanced fields near 10 to 200 nm gold nanospheres, driven by incident near infrared (NIR) or visible laser pulses. We model the gold conduction band in terms of a spherical square well potential. Our simulated streaked photoelectron spectra reveal a plasmonic amplitude enhancement and phase shift related to calculations that exclude the induced plasmonic field. The phase shift is due to the plasma resonance. This suggests the use of streaked photoelectron spectroscopy for imaging the dielectric response and plasmonic field near nanoparticles. Supported by the NSD-EPSCoR program, NSF, and the USDoE.

  20. Method for estimating ionicities of oxides using O1s photoelectron spectra

    NASA Astrophysics Data System (ADS)

    Wu, L. Q.; Li, Y. C.; Li, S. Q.; Li, Z. Z.; Tang, G. D.; Qi, W. H.; Xue, L. C.; Ge, X. S.; Ding, L. L.

    2015-09-01

    The average valence, ValO, of the oxygen anions in the perovskite oxide BaTiO3, was found using O1s photoelectron spectra to be -1.55. This experimental result is close to the theoretical value for BaTiO3 (-1.63) calculated by Cohen [Nature 358, 136 (1992)] using density functional theory. Using the same approach, we obtained values of ValO for several monoxides, and investigated the dependence of ValO and the ionicity on the second ionization energy, V(M2+), of the metal cation. We found that the dependence of the ionicity on V(M2+) in this work is close to that reported by Phillips [Rev. Mod. Phys. 42, 317 (1970)]. We therefore suggest that O1s photoelectron spectrum measurements should be accepted as a general experimental method for estimating the ionicity and average valence of oxygen anions.

  1. Inversion of strong-field photoelectron spectra for molecular orbital imaging

    NASA Astrophysics Data System (ADS)

    Puthumpally-Joseph, R.; Viau-Trudel, J.; Peters, M.; Nguyen-Dang, T. T.; Atabek, O.; Charron, E.

    2016-08-01

    Imaging structures at the molecular level is a developing interdisciplinary research field that spans the boundaries of physics and chemistry. High-spatial-resolution images of molecules can be obtained with photons or ultrafast electrons. In addition, images of valence molecular orbitals can be extracted via tomographic techniques based on the coherent extreme UV radiation emitted by a molecular gas exposed to an intense ultrashort infrared laser pulse. In this paper, we demonstrate that similar information can be obtained by inverting energy-resolved photoelectron spectra using a simplified analytical model.

  2. Electron-ion interaction effects in attosecond time-resolved photoelectron spectra

    SciTech Connect

    Zhang, C.-H.; Thumm, U.

    2010-10-15

    Photoionization by attosecond extreme ultraviolet (xuv) pulses into the laser-dressed continuum of the ionized atom is commonly described in strong-field approximation, neglecting the Coulomb interaction between the emitted photoelectron (PE) and the residual ion. By solving the time-dependent Schroedinger equation, we identify a temporal shift {delta}{tau} in streaked PE spectra, which becomes significant at low PE energies. Within an eikonal approximation, we trace this shift to the combined action of Coulomb and laser forces on the released PE, suggesting the experimental and theoretical scrutiny of their coupling in streaked PE spectra. Further, we examined the effect of initial state polarization by the laser pulse on the xuv streaked spectrum.

  3. Application of high-resolution photoelectron spectroscopy: Vibrational resolved C 1s and O 1s spectra of CO adsorbed on Ni(100)

    SciTech Connect

    Foehlisch, A.; Nilsson, A.; Martensson, N.

    1997-04-01

    There are various effects which determine the line shape of a core-level electron spectrum. These are due to the finite life-time of the core hole, inelastic scattering of the outgoing photoelectron, electronic shake-up and shake-off processes and vibrational excitations. For free atoms and molecules the different contributions to the observed line shapes can often be well separated. For solids, surfaces and adsorbates the line shapes are in general much broader and it has in the past been assumed that no separation of the various contributions can be made. In the present report the authors will show that this is indeed not the case. Surprisingly, the vibrational fine structure of CO adsorbed on Ni(100) can be resolved in the C 1s and O 1s electron spectra. This was achieved by the combination of highly monochromatized soft X-rays from B18.0 with a high resolution Scienta 200 mm photoelectron spectrometer. X-ray photoelectron spectroscopy (XPS) with tunable excitation energy yields as a core level spectroscopy atomic and site-specific information. The presented measurements allow for a determination of internuclear distances and potential energy curves in corehole ionized adsorbed molecules. The authors analysis of the c(2x2) phase CO/Ni(100) on {open_quotes}top{close_quotes} yielded a vibrational splitting of 217 +/- 2 meV for C 1s ionization. For O 1s ionization a splitting of 173 +/- 8 meV was found.

  4. Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

    SciTech Connect

    Grell, Gilbert; Bokarev, Sergey I. Kühn, Oliver; Winter, Bernd; Seidel, Robert; Aziz, Emad F.; Aziz, Saadullah G.

    2015-08-21

    X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H{sub 2}O){sub 6}]{sup 2+} complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

  5. Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Grell, Gilbert; Bokarev, Sergey I.; Winter, Bernd; Seidel, Robert; Aziz, Emad F.; Aziz, Saadullah G.; Kühn, Oliver

    2015-08-01

    X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H2O)6]2+ complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

  6. Is the Separable Propagator Perturbation Approach Accurate in Calculating Angle Resolved Photoelectron Diffraction Spectra?

    NASA Astrophysics Data System (ADS)

    Ng, C. N.; Chu, T. P.; Wu, Huasheng; Tong, S. Y.; Huang, Hong

    1997-03-01

    We compare multiple scattering results of angle-resolved photoelectron diffraction spectra between the exact slab method and the separable propagator perturbation method. In the slab method,footnote C.H. Li, A.R. Lubinsky and S.Y. Tong, Phys. Rev. B17, 3128 (1978). the source wave and multiple scattering within the strong scattering atomic layers are expanded in spherical waves while interlayer scattering is expressed in plane waves. The transformation between spherical waves and plane waves is done exactly. The plane waves are then matched across the solid-vacuum interface to a single outgoing plane wave in the detector's direction. The separable propagator perturbation approach uses two approximations: (i) A separable representation of the Green's function propagator and (ii) A perturbation expansion of multiple scattering terms. Results of c(2x2) S-Ni(001) show that this approximate method fails to converge due to the very slow convergence of the separable representation for scattering angles less than 90^circ. However, this method is accurate in the backscattering regime and may be applied to XAFS calculations.(J.J. Rehr and R.C. Albers, Phys. Rev. B41, 8139 (1990).) The use of this method for angle-resolved photoelectron diffraction spectra is substantially less reliable.

  7. Structural investigation on Ge{sub x}Sb{sub 10}Se{sub 90−x} glasses using x-ray photoelectron spectra

    SciTech Connect

    Wei, Wen-Hou; Xiang, Shen; Xu, Si-Wei; Wang, Rong-Ping; Fang, Liang

    2014-05-14

    The structure of Ge{sub x}Sb{sub 10}Se{sub 90−x} glasses (x = 7.5, 10, 15, 20, 25, 27.5, 30, and 32.5 at. %) has been investigated by x-ray photoelectron spectroscopy (XPS). Different structural units have been extracted and characterized by decomposing XPS core level spectra, the evolution of the relative concentration of each structural unit indicates that, the relative contributions of Se-trimers and Se-Se-Ge(Sb) structure decrease with increasing Ge content until they become zero at chemically stoichiometric glasses of Ge{sub 25}Sb{sub 10}Se{sub 65}, and then the homopolar bonds like Ge-Ge and Sb-Sb begin to appear in the spectra. Increase of homopolar bonds will extend band-tails into the gap and narrow the optical band gap. Thus, the glass with a stoichiometric composition generally has fewer defective bonds and larger optical bandgap.

  8. Asymmetries in transition metal XPS spectra: metal nanoparticle structure, and interaction with the graphene-structured substrate surface.

    PubMed

    Sacher, E

    2010-03-16

    Transition-metal XPS spectra have traditionally been considered to possess a natural asymmetry, extending to the high-binding-energy side. This is based on the fact that these spectra have generally been found experimentally to have such an asymmetry, as well as on the confirmation of asymmetry offered by the Doniach-Sunjić equation, an equation based on the proposal that the conduction electron scattering amplitude for interband absorption or emission in metals, at the Fermi level, is a singularity. Our discovery that metal nanoparticles, prepared under vacuum and characterized without exposure to air, have symmetric peaks, which become asymmetric with time, informed us that these peak asymmetries have other sources. On the basis of our belief that all metal spectra are composed of symmetric peaks, where the asymmetries are attributed to overlapping minor peaks that are consistent with known physical and chemical phenomena associated with that metal, we have shown that, for the metals that we have studied, these asymmetries contain much information, otherwise unavailable, on the structures, contaminants, oxidation, and interfacial interactions of nanoparticle surfaces. The existence of this information has been demonstrated for several metals, and its value is shown by its use in explaining the strong interfacial bonding of the nanoparticles with substrates having graphene structures. A possible future research direction is offered in the field of metal-metal interactions in nanoparticle alloys.

  9. Method for estimating ionicities of oxides using O1s photoelectron spectra

    SciTech Connect

    Wu, L. Q.; Li, Z. Z.; Tang, G. D. Qi, W. H.; Xue, L. C.; Ge, X. S.; Ding, L. L.; Li, Y. C.; Li, S. Q.

    2015-09-15

    The average valence, V{sub alO}, of the oxygen anions in the perovskite oxide BaTiO{sub 3}, was found using O1s photoelectron spectra to be −1.55. This experimental result is close to the theoretical value for BaTiO{sub 3} (−1.63) calculated by Cohen [Nature 358, 136 (1992)] using density functional theory. Using the same approach, we obtained values of V{sub alO} for several monoxides, and investigated the dependence of V{sub alO} and the ionicity on the second ionization energy, V(M{sup 2+}), of the metal cation. We found that the dependence of the ionicity on V(M{sup 2+}) in this work is close to that reported by Phillips [Rev. Mod. Phys. 42, 317 (1970)]. We therefore suggest that O1s photoelectron spectrum measurements should be accepted as a general experimental method for estimating the ionicity and average valence of oxygen anions.

  10. Infrared and x-ray photoelectron spectra of ruthenium oxide films and ruthenium hydroxide

    SciTech Connect

    Belova, I.D.; Shifrina, R.R.; Roginskaya, Yu.E.; Popov, A.V.; Varlamova, T.V.

    1988-03-01

    The IR and x-ray photoelectron spectra of ruthenium hydroxide and of ruthenium oxide films produced by ruthenium chloride hydroxide decomposition at 300, 400, 500, and 600 degrees C were examined in order to obtain information concerning the effect of hydration on the structure and electronic properties of the surface of ruthenium oxide electrodes. It was shown that Ru hydroxide and Ru oxide films contain both water molecules and hydroxyl groups; the latter are retained up to higher temperatures (600 degrees C) in the Ru oxide films than in Ru hydroxide. It was found that water makes the materials studied amorphous, and it also was found that hydration influences their electronic structure (valence band and the electronic core levels of Ru and O).

  11. Comparison of hard and soft x-ray photoelectron spectra of silicon

    NASA Astrophysics Data System (ADS)

    Offi, F.; Werner, W. S. M.; Sacchi, M.; Torelli, P.; Cautero, M.; Cautero, G.; Fondacaro, A.; Huotari, S.; Monaco, G.; Paolicelli, G.; Smekal, W.; Stefani, G.; Panaccione, G.

    2007-08-01

    A detailed comparison of the surface sensitivity of x-ray photoemission spectroscopy for hard and soft x rays is presented and discussed. Electron scattering parameters and their energy dependence are given for Si and two Si spectra are analyzed: a MgKα (hν=1253.6eV) excited spectrum of the Si2p and 2s lines and a hard x-ray excited spectrum (hν=5925eV) of the Si1s line. The differential inelastic scattering characteristics for Si are extracted from reflection electron energy loss spectra taken at energies of 1500 and 4000eV . Using these scattering characteristics and electron mean free paths from the literature, simulated spectra are compared with experiment. The experimental spectra are deconvoluted to give the true intrinsic line shape corresponding to the theoretical collision statistics when interference effects between intrinsic and extrinsic scattering are neglected. The magnitude of interference effects cannot be assessed by our analysis. Within the (unknown) uncertainty introduced by neglecting interference effects, it is possible to determine the relative intensity of intrinsic and extrinsic excitations. In this way, it is found that in the case of the soft x-ray excited photoelectron spectrum of the shallower electronic shells ( 2p and 2s ), intrinsic plasmon creation is rather weak, and the apparent asymmetric line shape of the spectrum might be interpreted as the fact that electron-hole pair creation dominates the intrinsic loss spectrum, while an alternative explanation in terms of surface core level shifted components is also proposed. For the deeper core electronic shell, probed with hard x rays, the opposite situation is observed: while intrinsic electron-hole pair creation was not observed, a strong contribution of intrinsic plasmon losses of about 30% was seen.

  12. Theoretical study of IR and photoelectron spectra of small gallium-arsenide clusters

    SciTech Connect

    Pouchan, Claude; Marchal, Rémi; Hayashi, Shinsuke

    2015-01-22

    Relative stabilities of small Ga{sub n}As{sub m} clusters, as well as their structural electronic and vibrational properties, were computed and analysed using a CCSD(T) reference method since experimental data in this area are sparse or unknown. With the aim of investigating larger clusters, we explored several DFT functionals and basis sets able to mimic the reliable CCSD(T) approach. Among them, the PBE0/SBKJC+sp,d appears as the most efficient to describe the structural and vibrational properties since average differences of about 0.042Å and 5.1cm{sup −1} were obtained for bond lengths and fundamental vibrational frequencies, respectively for the first small clusters [1] of the series found from our GSAM method [2]. As further test, this model is used in order to investigate and revisit an experimental IR spectrum of Ga{sub n}As{sub m} mixture previously published by Li et al. [3]. More complicated is the difficulty which arises in the electronic description due to the presence of numerous low lying electronic states nearly degenerated to correctly describe the electronic structure. The case of Ga{sub 2}As will be discussed and the photoelectron spectra of the Ga{sub 2}As anion reanalyzed on the ground of our calculations [4] comparatively to the experimental spectra obtained by Neumark and co-workers [5].

  13. [Active oxygen species of Co-V-O catalysts in propane oxidative dehydrogenation analyzed by FTIR and XPS spectra].

    PubMed

    Xu, Ai-Ju; Lin, Qin; Bao, Zhaorigetu; Jia, Mei-Lin; Liu, Lian-Yun

    2009-02-01

    A series of Co-V-O (meta-CoV2O6, pyro-Co2 V2 O7, and ortho-Co3 V2 O8) catalysts were prepared by microwave oxalate co-precipitation method and characterized by (XRD), TEM, BET, FTIR, XPS, H2-TPR and conductivity measurement. The catalytic characters of the catalysts for propane oxidative dehydrogenation were investigated. The FTIR spectra of catalysts were obtained in the range of 400-1 100 cm(-1) and their major bands were assigned. The peak separation fitting of O(1s) XPS spectra was carried out and the quantity of oxygen species was calculated. The results of XRD characterization showed that pure meta-CoV2O6, pyro-Co2 V2O7, and ortho-Co3 V2O8 with nice structure were obtained. The TEM images demonstrated that the catalysts showed uniform particle with the mean particle size of 20-30 nm. The diagram of the relationship between electrical conductivity and oxygen partial pressure of Co3V2O8 and Co2 V2O7 showed dsigma/dPo2 > 0, which implied that these were p-type semiconductor, and CoV2O6 reverse showed dsigma/dPo2 < 0, which implied n-type semiconductor. 48.12%, 47.82% and 35.24% of C3 H6 selectivities were obtained for p-type semiconductor Co3 V2O8, CO2 V2O7 and n-type CoV2O6 catalysts respectively at 10% C3H6 conversion, and the results showed that p-type semiconductor catalysts Co3 V2O8 and Co2 V2O7 showed higher activity than n-type catalyst CoV2O6. The results of FTIR, XPS, H2-TPR and conductivity measurement indicated that transferring between non-stoichiometric and lattice oxygen that easily happened in Co3 V2O8 and Co2 V2O7 catalysts might promote the oxidation-reduction reaction between different valence vanadium species, and promoted the oxygen vacancy formation. Furthermore, the forming of Co-O-V bridge bond that was easy to shift between Co and V increased the mobile oxygen species of O2-, O2(2-) and O- and made the redox reaction among different valence V be realized. It is concluded that high catalytic properties of p-type semiconductor Co3 V2O8 and

  14. Photoelectron spectra of CeO{sup −} and Ce(OH){sub 2}{sup −}

    SciTech Connect

    Ray, Manisha; Felton, Jeremy A.; Kafader, Jared O.; Topolski, Josey E.; Jarrold, Caroline Chick

    2015-02-14

    The photoelectron spectrum of CeO{sup −} exhibits what appears to be a single predominant electronic transition over an energy range in which numerous close-lying electronic states of CeO neutral are well known. The photoelectron spectrum of Ce(OH){sub 2}{sup −}, a molecule in which the Ce atom shares the same formal oxidation state as the Ce atom in CeO{sup −}, also exhibits what appears to be a single transition. From the spectra, the adiabatic electron affinities of CeO and Ce(OH){sub 2} are determined to be 0.936 ± 0.007 eV and 0.69 ± 0.03 eV, respectively. From the electron affinity of CeO, the CeO{sup −} bond dissociation energy was determined to be 7.7 eV, 0.5 eV lower than the neutral bond dissociation energy. The ground state orbital occupancies of both CeO{sup −} and Ce(OH){sub 2}{sup −} are calculated to have 4f 6s{sup 2} Ce{sup +} superconfigurations, with open-shell states having 4f5d6s superconfiguration predicted to be over 1 eV higher in energy. Low-intensity transitions observed at higher electron binding energies in the spectrum of CeO{sup −} are tentatively assigned to the {sup 1}Σ{sup +} (Ω = 0) state of CeO with the Ce{sup +2}⍰6s{sup 2} superconfiguration.

  15. Ab Initio Determinations of Photoelectron Spectra Including Vibronic Features: An Upper-Level Undergraduate Physical Chemistry Laboratory

    ERIC Educational Resources Information Center

    Lord, Richard L.; Davis, Lisa; Millam, Evan L.; Brown, Eric; Offerman, Chad; Wray, Paul; Green, Susan M. E.

    2008-01-01

    We present a first-principles determination of the photoelectron spectra of water and hypochlorous acid as a laboratory exercise accessible to students in an undergraduate physical chemistry course. This paper demonstrates the robustness and user-friendliness of software developed for the Franck-Condon factor calculation. While the calculator is…

  16. X-ray photoelectron spectra structure and chemical bond nature in NpO2

    NASA Astrophysics Data System (ADS)

    Teterin, Yu. A.; Teterin, A. Yu.; Ivanov, K. E.; Ryzhkov, M. V.; Maslakov, K. I.; Kalmykov, St. N.; Petrov, V. G.; Enina, D. A.

    2014-01-01

    Quantitative analysis was done of the x-ray photoelectron spectra structure in the binding energy (BE) range of 0 to ˜35 eV for neptunium dioxide (NpO2) valence electrons. The BEs and structure of the core electronic shells (˜35-1250 eV) as well as the relativistic discrete variation calculation results for the finite fragment of the NpO2 lattice and the data of other authors were taken into account. The experimental data show that the many-body effects and the multiplet splitting contribute to the spectral structure much less than the effects of formation of the outer (0-˜15 eV) and the inner (˜15-˜35 eV) valence molecular orbitals (OVMO and IVMO, respectively). The filled Np 5f electronic states were shown to form in the NpO2 valence band. The Np 6p electrons participate in formation of both the IVMO and the OVMO (bands). The filled Np 6p3/2 and the O 2s electronic shells were found to take the maximum part in the IVMO formation. The MO composition and the sequence order in the BE range 0-˜35 eV in NpO2 were established. The experimental and theoretical data allowed a quantitative MO scheme for NpO2, which is fundamental for both understanding the chemical bond nature in neptunium dioxide and the interpretation of other x-ray spectra of NpO2.

  17. Ultraviolet photoelectron spectra of mono-metal endohedral fullerene Er@C 82 (I)

    NASA Astrophysics Data System (ADS)

    Miyazaki, Takafumi; Sumii, Ryohei; Umemoto, Hisashi; Okimoto, Haruya; Ito, Yasuhiro; Sugai, Toshiki; Shinohara, Hisanori; Hino, Shojun

    2010-12-01

    Ultraviolet photoelectron spectra (UPS) of Erbium endohedral fullerene Er@C 82 (I) were measured using a synchrotron radiation light source. The spectral onset of Er@C 82 (I) was 0.4 eV, which is smaller than those of divalent atom endohedral metallofullerenes and analogous to those of trivalent atom endohedral metallofullerenes. The upper valence structure ( Eb < 5 eV) of Er@C 82 (I) was almost identical with those of C 2v-Tb@C 82 and C 2v-La@C 82. The oxidation states of Er in Er@C 82 from the analogy of the oxidation state of Tb in Tb@C 82 and La in La@C 82 is estimated to be +3. The UPS of Er@C 82 (I) differs from those of Tm@C 82 isomers. The reason of the difference is attributed to differences in their cage structures and oxidation states. The upper valence UPS of Er@C 82 (I) could be well reproduced by a simulated spectrum obtained with a Gaussian03 program module assuming C 82-C 2v cage structure with three additional electrons.

  18. Vibrational branching ratios in the photoelectron spectra of N2 and CO: interference and diffraction effects.

    PubMed

    Plésiat, Etienne; Decleva, Piero; Martín, Fernando

    2012-08-21

    We present a detailed account of existing theoretical methods specially designed to provide vibrationally resolved photoionization cross sections of simple molecules within the Born-Oppenheimer approximation, with emphasis on newly developed methods based on density functional theory. The performance of these methods is shown for the case of N(2) and CO photoionization. Particular attention is paid to the region of high photon energies, where the electron wavelength is comparable to the bond length and, therefore, two-center interferences and diffraction are expected to occur. As shown in a recent work [Canton et al., Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 7302-7306], the main experimental difficulty, which is to extract the relatively small diffraction features from the rapidly decreasing cross section, can be easily overcome by determining ratios of vibrationally resolved photoelectron spectra and existing theoretical calculations. From these ratios, one can thus get direct information about the molecular geometry. In this work, results obtained in a wide range of photon energies and for many different molecular orbitals of N(2) and CO are discussed and compared with the available experimental measurements. From this comparison, limitations and further possible improvements of the existing theoretical methods are discussed. The new results presented in the manuscript confirm that the conclusions reported in the above reference are of general validity.

  19. Ultraviolet photoelectron spectra of (YC)2 @ C82 and Y2 @ C82

    NASA Astrophysics Data System (ADS)

    Hino, Shojun; Wanita, Norihiko; Iwasaki, Kentaro; Yoshimura, Daisuke; Akachi, Takao; Inoue, Takeshi; Ito, Yasuhiro; Sugai, Toshiki; Shinohara, Hisanori

    2005-11-01

    Ultraviolet photoelectron spectra (UPS) of metallofullerenes, (YC)2@C82 (III) and Y2@C82 (III) were measured using a synchrotron radiation light source. The spectral onset energy of (YC)2@C82 (III) was determined to be 0.8 eV below the Fermi level, and that of Y2@C82 (III) was 0.45eV , indicating the semiconductive nature of these metallofullerenes. The UPS consisted of numerous crests and troughs. Further, a change in intensity upon tuning the excitation energy was observed; however, the intensity of the change was not as large as those observed for other fullerenes. The UPS of two metallofullerenes basically resemble each other, although there are minute differences between them. The UPS of (YC)2@C82 (III) was easily reproduced by a simulated spectrum obtained by molecular orbital calculations assuming a C3v (8) cage structure with four additional electrons on the cage. A difference spectrum between the UPS of (YC)2@C82 (III) and Y2@C82 (III) indicates the existence of additional electrons on the cage of Y2@C82 .

  20. Extreme ultraviolet ionization of pure He nanodroplets: mass-correlated photoelectron imaging, Penning ionization, and electron energy-loss spectra.

    PubMed

    Buchta, D; Krishnan, S R; Brauer, N B; Drabbels, M; O'Keeffe, P; Devetta, M; Di Fraia, M; Callegari, C; Richter, R; Coreno, M; Prince, K C; Stienkemeier, F; Ullrich, J; Moshammer, R; Mudrich, M

    2013-08-28

    The ionization dynamics of pure He nanodroplets irradiated by Extreme ultraviolet radiation is studied using Velocity-Map Imaging PhotoElectron-PhotoIon COincidence spectroscopy. We present photoelectron energy spectra and angular distributions measured in coincidence with the most abundant ions He(+), He2(+), and He3(+). Surprisingly, below the autoionization threshold of He droplets, we find indications for multiple excitation and subsequent ionization of the droplets by a Penning-like process. At high photon energies we observe inelastic collisions of photoelectrons with the surrounding He atoms in the droplets.

  1. Vibrationally high-resolved electronic spectra of MCl2 (M = C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl2-

    NASA Astrophysics Data System (ADS)

    Ran, Yibin; Pang, Min; Shen, Wei; Li, Ming; He, Rongxing

    2016-10-01

    We systematically studied the vibrational-resolved electronic spectra of group IV dichlorides using the Franck-Condon approximation combined with the Duschinsky and Herzberg-Teller effects in harmonic and anharmonic frameworks (only the simulation of absorption spectra includes the anharmonicity). Calculated results showed that the band shapes of simulated spectra are in accordance with those of the corresponding experimental or theoretical ones. We found that the symmetric bend mode in progression of absorption is the most active one, whereas the main contributor in photoelectron spectra is the symmetric stretching mode. Moreover, the Duschinsky and anharmonic effects exert weak influence on the absorption spectra, except for PbCl2 molecule. The theoretical insights presented in this work are significant in understanding the photophysical properties of MCl2 (M = C, Si, Ge, Sn, Pb) and studying the Herzberg-Teller and the anharmonic effects on the absorption spectra of new dichlorides of this main group.

  2. Deduction of the chemical state and the electronic structure of Nd{sub 2}Fe{sub 14}B compound from X-ray photoelectron spectroscopy core-level and valence-band spectra

    SciTech Connect

    Wang, Jing; Liang, Le; Zhang, Lanting E-mail: lmsun@sjtu.edu.cn; Sun, Limin E-mail: lmsun@sjtu.edu.cn; Hirano, Shinichi

    2014-10-28

    Characterization of chemical state and electronic structure of the technologically important Nd{sub 2}Fe{sub 14}B compound is attractive for understanding the physical nature of its excellent magnetic properties. X-ray photoelectron spectroscopy (XPS) study of such rare-earth compound is important and also challenging due to the easy oxidation of surface and small photoelectron cross-sections of rare-earth 4f electrons and B 2p electrons, etc. Here, we reported an investigation based on XPS spectra of Nd{sub 2}Fe{sub 14}B compound as a function of Ar ion sputtering time. The chemical state of Fe and that of B in Nd{sub 2}Fe{sub 14}B compound can be clearly determined to be 0 and −3, respectively. The Nd in Nd{sub 2}Fe{sub 14}B compound is found to have the chemical state of close to +3 instead of +3 as compared with the Nd in Nd{sub 2}O{sub 3}. In addition, by comparing the valence-band spectrum of Nd{sub 2}Fe{sub 14}B compound to that of the pure Fe, the contributions from Nd, Fe, and B to the valence-band structure of Nd{sub 2}Fe{sub 14}B compound is made more clear. The B 2p states and B 2s states are identified to be at ∼11.2 eV and ∼24.6 eV, respectively, which is reported for the first time. The contribution from Nd 4f states can be identified both in XPS core-level spectrum and XPS valence-band spectrum. Although Nd 4f states partially hybridize with Fe 3d states, Nd 4f states are mainly localized in Nd{sub 2}Fe{sub 14}B compound.

  3. On-the-Fly ab Initio Semiclassical Dynamics of Floppy Molecules: Absorption and Photoelectron Spectra of Ammonia.

    PubMed

    Wehrle, Marius; Oberli, Solène; Vaníček, Jiří

    2015-06-01

    We investigate the performance of on-the-fly ab initio (OTF-AI) semiclassical dynamics combined with the thawed Gaussian approximation (TGA) for computing vibrationally resolved absorption and photoelectron spectra. Ammonia is used as a prototype of floppy molecules, whose potential energy surfaces display strong anharmonicity. We show that despite complications due to the presence of large amplitude motion, the main features of the spectra are captured by the OTF-AI-TGA, which—by definition—does not require any a priori knowledge of the potential energy surface. Moreover, the computed spectra are significantly better than those based on the popular global harmonic approximation. Finally, we probe the limit of the TGA to describe higher-resolution spectra, where long time dynamics is required. PMID:25928833

  4. Application of XPS to study electrocatalysts for fuel cells

    NASA Astrophysics Data System (ADS)

    Corcoran, C. J.; Tavassol, H.; Rigsby, M. A.; Bagus, P. S.; Wieckowski, A.

    Analysis of the surface is paramount to understanding the reactivity, selectivity, and catalytic ability of substances. In particular, this understanding is required to make an efficient use of the catalytic surfaces in fuel cells. X-ray photoelectron spectroscopy (XPS) allows determination of changes in the electronic structure for different surface preparation and composition based, mainly, on shifts of the binding energies of core-level electrons. It is also an ideal method that allows identification of the surface or near surface species in relation to fuel cell catalysis. However, the fundamental theoretical concepts, which are used to analyze and interpret XPS spectra are sometimes not correctly understood or correctly applied. In this review, we not only report on XPS operational parameters in use for fuel cell electrocatalysis, but, more significantly, we review and provide rigorous definitions of fundamental concepts used to understand XPS spectra, including the separation of initial and final state effects and the relaxation of valence electrons to screen core-holes. An additional direction of our review is to show the relationships between XPS binding energy shifts and XPS satellite structure with chemical bonding and chemical interactions. However, our primary concern is to provide reviews of representative cases of the application of XPS to solving fuel cell and electrocatalysis-related problems, highlighting progress in this laboratory. We begin with descriptions of essential issues in fuel cell science and with a review of key concepts of XPS. Then, we briefly report on the XPS instrumentation, after which, studies of fundamental importance to electrochemical processes are reviewed. This review includes an overview of complex organic and biological systems in relation to fuel cell electrocatalysis (probed via XPS). We conclude with a discussion of modern developments in XPS methodology.

  5. A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

    SciTech Connect

    Powell, C.J.; Smekal, W.; Werner, W.S.M.

    2005-09-09

    We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. We report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.

  6. A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

    NASA Astrophysics Data System (ADS)

    Powell, C. J.; Smekal, W.; Werner, W. S. M.

    2005-09-01

    We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. We report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.

  7. Nonadiabatic dynamics and simulation of time resolved photoelectron spectra within time-dependent density functional theory: Ultrafast photoswitching in benzylideneaniline

    SciTech Connect

    Mitric, Roland; Werner, Ute; Bonacic-Koutecky, Vlasta

    2008-10-28

    We present a theoretical approach for the nonadiabatic dynamics 'on the fly' based on the combination of the time-dependent density functional theory (TDDFT) with Tully's stochastic surface hopping method. Our formulation is based on localized Gaussian basis sets and is suitable for the simulation of ultrafast processes in complex molecular systems including all degrees of freedom. Our approach is used for the simulation of time resolved photoelectron spectra in the framework of the Wigner distribution approach. In order to illustrate the scope of the method, we study the ultrafast photoswitching dynamics of the prototype Schiff base benzylideneaniline (BAN). The nonradiative lifetime of the S{sub 1} state of BAN is determined to be {approx}200 fs. The mechanism of the photoisomerization has been investigated and a connection between the time resolved photoelectron signal and the underlying nonadiabatic processes has been established.

  8. The influence of oxygen adsorption on the NEXAFS and core-level XPS spectra of the C{sub 60} derivative PCBM

    SciTech Connect

    Brumboiu, Iulia Emilia Eriksson, Olle; Brena, Barbara; Ericsson, Leif; Hansson, Rickard; Moons, Ellen

    2015-02-07

    Fullerenes have been a main focus of scientific research since their discovery due to the interesting possible applications in various fields like organic photovoltaics (OPVs). In particular, the derivative [6,6]-phenyl-C{sub 60}-butyric acid methyl ester (PCBM) is currently one of the most popular choices due to its higher solubility in organic solvents compared to unsubstituted C{sub 60}. One of the central issues in the field of OPVs is device stability, since modules undergo deterioration (losses in efficiency, open circuit voltage, and short circuit current) during operation. In the case of fullerenes, several possibilities have been proposed, including dimerization, oxidation, and impurity related deterioration. We have studied by means of density functional theory the possibility of oxygen adsorption on the C{sub 60} molecular moiety of PCBM. The aim is to provide guidelines for near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) measurements which can probe the presence of atomic or molecular oxygen on the fullerene cage. By analysing several configurations of PCBM with one or more adsorbed oxygen atoms, we show that a joint core level XPS and O1s NEXAFS investigation could be effectively used not only to confirm oxygen adsorption but also to pinpoint the bonding configuration and the nature of the adsorbate.

  9. ATOMIC AND MOLECULAR PHYSICS: Theoretical Investigation of Femtosecond-Resolved Photoelectron Spectra of the Li2 Molecule

    NASA Astrophysics Data System (ADS)

    Liu, Yu-Fang; Liu, Rui-Qiong; Ding, Jun-Xia

    2009-07-01

    The time-dependent quantum wave packet method is used to investigate the dynamics for the Li2 molecule, and the time-resolved photoelectron spectra (TRPES) of the Li2 molecule are calculated. At the short delay time, the particular phenomenon of TRPES with four peaks is qualitatively interpreted in a dressed state picture by analyzing wave packet motion on light-induced potential (LIP). The significant difference in the electronic structure of between the inner and outer turning points has an impact on the TRPES. The control for the first excited state of the initial wave packet is discussed.

  10. XPS analysis of humic and fulvic acids

    SciTech Connect

    Desbene, P.L.; Silly, L.; Morizur, J.P.; Delamar, M.

    1986-01-01

    The composition of humic and fulvic acids is examined using X-ray Photoelectron Spectroscopy (XPS). The XPS results are compared to that of elemental analyses. XPS permits an easy detection of the different chemical forms of carbon and sulfur that exist in these complex compounds.

  11. Exploring Ultrafast Molecular Dynamics using Photoelectron Spectra from UV/XUV Pump-Probe Experiments

    NASA Astrophysics Data System (ADS)

    Champenois, Elio; Cryan, James; Shivaram, Niranjan; Wright, Travis; Belkacem, Ali

    2015-05-01

    The motion of atoms in molecules can drive electron dynamics via non-adiabatic couplings. In small molecules such as Ethylene, Carbon Dioxide, and Nitrophenol, this can lead to isomerization, electronic relaxation, or other time-dependent effects following excitation from a bonding to an anti-bonding molecular orbital. To study these mechanisms, we use ultraviolet photons of various energies from a bright High Harmonic Generation source to first initiate dynamics and subsequently probe the system through ionization. We record the kinetic energy and angular distribution of the resultant photoelectrons using a Velocity Map Imaging spectrometer, allowing us to track the evolution of the electronic state.

  12. Surface structure of [XMIm]Tf2N ultrathin ionic liquid films probed by metastable He atoms and photoelectron spectroscopies (UPS and XPS)

    NASA Astrophysics Data System (ADS)

    Krischok, S.; Ulbrich, A.; Ikari, T.; Kempter, V.; Marschewski, M.; Höfft, O.

    2014-12-01

    The metastable induced electron spectroscopy (MIES), in combination with photoelectron spectroscopies, is a powerful tool to analyze the molecular arrangement at surfaces due to its high surface sensitivity. In this contribution MIES is applied to analyze structural changes at the surface of [EMIm]Tf2N and [OMIm]Tf2N films on two different substrates, Highly Ordered Pyrolytic Graphite (HOPG) and Au(111), as a function of the film thickness, starting from submonolayer coverage up to multilayers. The discussion is based on previous MIES studies of the vacuum-liquid interface of ionic liquids with imidazolium cations and on available DFT calculations. The presented data indicate that - in contrast to multilayers where the surface is dominated by the alkyl chains of the imidazolium cations - the structure of the first adlayer of [XMIm]Tf2N molecules on solid surfaces depends on the strength of their interaction with the surface resulting in alkyl chains aligned parallel or oblique to the substrate surface.

  13. Investigation of x-ray photoelectron spectroscopic (XPS), cyclic voltammetric analyses of WO3 films and their electrochromic response in FTO/WO3/electrolyte/FTO cells

    NASA Astrophysics Data System (ADS)

    Sivakumar, R.; Gopalakrishnan, R.; Jayachandran, M.; Sanjeeviraja, C.

    2006-06-01

    Electrochromic thin films of tungsten oxide (WO3) were prepared on transparent conducting oxide substrates, i.e., fluorine doped tin oxide coated (FTO or SnO2:F) glass and microscopic glass substrates by the electron beam evaporation technique using pure WO3 (99.99%) pellets at various substrate temperatures (i.e., Tsub = room temperature (RT, 30 °C), 100 °C and 200 °C). The films were prepared under vacuum of the order of 1 × 10-5 mbar. The room temperature prepared films were further post-heat-treated (Tanne) at 200 and 300 °C for about 1 h in the vacuum environment. The prepared films are in monoclinic phase. The chemical composition has been characterized by using the XPS technique. The W 4f and O 1s core levels of WO3 films have been studied on the samples. The obtained core level binding energies revealed the WO3 films contained six-valent tungsten (W6+). The electrochemical nature of the films was studied by a three-electrode electrochemical cell in the configuration of FTO/WO3/H2SO4/Pt, SCE, using the cyclic voltammetry (CV) technique. Electrochromic devices (ECDs) of the general type FTO/WO3/electrolyte/FTO were studied. The films produced at higher substrate temperature show smaller modulation of the visible spectrum, compared with the films produced at lower temperatures. The significant chemical bonding nature associated with the coloring/bleaching process which follows the H+ ion incorporation in the film is studied by FTIR analysis. The W-O-W framework peak was observed at 563 cm-1 and confirms the stability of the films in the electrochemical analysis. The results obtained from cyclic voltammetry technique and ECD cell characterization are used to emphasize the suitability for some applications of the solar control systems.

  14. Photoelectron spectra and structure of the Mn{sub n}{sup −} anions (n = 2–16)

    SciTech Connect

    Gutsev, G. L. Weatherford, C. A.; Ramachandran, B. R.; Gutsev, L. G.; Zheng, W.-J.; Thomas, O. C.; Bowen, Kit H.

    2015-07-28

    Photoelectron spectra of the Mn{sub n}{sup −} anion clusters (n = 2–16) are obtained by anion photoelectron spectroscopy. The electronic and geometrical structures of the anions are computed using density functional theory with generalized gradient approximation and a basis set of triple-ζ quality. The electronic and geometrical structures of the neutral Mn{sub n} clusters have also been computed to estimate the adiabatic electron affinities. The average absolute difference between the computed and experimental vertical detachment energies of an extra electron is about 0.2 eV. Beginning with n = 6, all lowest total energy states of the Mn{sub n}{sup −} anions are ferrimagnetic with the spin multiplicities which do not exceed 8. The computed ionization energies of the neutral Mn{sub n} clusters are in good agreement with previously obtained experimental data. According to the results of our computations, the binding energies of Mn atoms are nearly independent on the cluster charge for n > 6 and possess prominent peaks at Mn{sub 13} and Mn{sub 13}{sup −} in the neutral and anionic series, respectively. The density of states obtained from the results of our computations for the Mn{sub n}{sup −} anion clusters show the metallic character of the anion electronic structures.

  15. Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of HCl via the F 1Δ2 Rydberg state

    NASA Astrophysics Data System (ADS)

    Wang, Kwanghsi; McKoy, V.

    1991-12-01

    Results of studies of rotational ion distributions in the X 2Π3/2 and X 2Π1/2 spin-orbit states of HCl+ resulting from (2+1') resonance enhanced multiphoton ionization (REMPI) via the S(0) branch of the F 1Δ2 Rydberg state are reported and compared with measured threshold-field-ionization zero-kinetic-energy spectra reported recently [K. S. Haber, Y. Jiang, G. Bryant, H. Lefebvre-Brion, and E. R. Grant, Phys. Rev. A (in press)]. These results show comparable intensities for J+=3/2 of the X 2Π3/2 ion and J+=1/2 of the X 2Π1/2 ion. Both transitions require an angular momentum change of ΔN=-1 upon photoionization. To provide further insight into the near-threshold dynamics of this process, we also show rotationally resolved photoelectron angular distributions, alignment of the ion rotational levels, and rotational distributions for the parity components of the ion rotational levels. About 18% population is predicted to occur in the (+) parity component, which would arise from odd partial-wave contributions to the photoelectron matrix element. This behavior is similar to that in (2+1) REMPI via the S(2) branch of the F 1Δ2 state of HBr and was shown to arise from significant l mixing in the electronic continuum due to the nonspherical molecular ion potential. Rotational ion distributions resulting from (2+1) REMPI via the S(10) branch of the F 1Δ2 state are also shown.

  16. Two-center interference in molecular photoelectron energy spectra with intense attosecond circularly polarized XUV laser pulses

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Bian, Xue-Bin; Bandrauk, André D.

    2014-08-01

    We study two-center electron interference in molecular photoionization processes by intense attosecond circularly polarized extreme ultraviolet (XUV) laser pulses in both symmetric H2+ and nonsymmetric HHe2+ one-electron diatomic systems. Simulations from numerical solutions of time-dependent Schrödinger equations for the oriented symmetric molecular ion H2+ exhibit a signature of interference with double peaks (minima) in molecular attosecond photoelectron energy spectra (MAPES) at critical angles ϑc between the continuum electron momentum pe and the molecular internuclear R axis. The interference patterns are shown to be influenced by the molecular Coulomb potential, leading to a shift of the critical angle ϑc. Dependence of the two-center interference on the pulse ellipticity is also investigated. Furthermore, it is found that the interference phenomena are critically sensitive to the molecular orbital symmetry. For the nonsymmetric molecular ion HHe2+, such double peaks in MAPES also occur, thus suggesting a method for imaging orbitals in molecules by intense ultrashort circularly polarized XUV pulses on the attosecond time scale.

  17. Sample-morphology effects on x-ray photoelectron peak intensities. III. Simulated spectra of model core–shell nanoparticles

    SciTech Connect

    Powell, Cedric J.; Chudzicki, Maksymilian; Werner, Wolfgang S. M.; Smekal, Werner

    2015-09-15

    The National Institute of Standards and Technology database for the simulation of electron spectra for surface analysis has been used to simulate Cu 2p photoelectron spectra for four types of spherical copper–gold nanoparticles (NPs). These simulations were made to extend the work of Tougaard [J. Vac. Sci. Technol. A 14, 1415 (1996)] and of Powell et al. [J. Vac. Sci. Technol. A 31, 021402 (2013)] who performed similar simulations for four types of planar copper–gold films. The Cu 2p spectra for the NPs were compared and contrasted with analogous results for the planar films and the effects of elastic scattering were investigated. The new simulations were made for a monolayer of three types of Cu/Au core–shell NPs on a Si substrate: (1) an Au shell of variable thickness on a Cu core with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm; (2) a Cu shell of variable thickness on an Au core with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm; and (3) an Au shell of variable thickness on a 1 nm Cu shell on an Au core with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm. For these three morphologies, the outer-shell thickness was varied until the Cu 2p{sub 3/2} peak intensity was the same (within 2%) as that found in our previous work with planar Cu/Au morphologies. The authors also performed similar simulations for a monolayer of spherical NPs consisting of a CuAu{sub x} alloy (also on a Si substrate) with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm. In the latter simulations, the relative Au concentration (x) was varied to give the same Cu 2p{sub 3/2} peak intensity (within 2%) as that found previously. For each morphology, the authors performed simulations with elastic scattering switched on and off. The authors found that elastic-scattering effects were generally strong for the Cu-core/Au-shell and weak for the Au-core/Cu-shell NPs; intermediate elastic-scattering effects were found for the Au-core/Cu-shell/Au-shell NPs. The shell thicknesses required to give

  18. Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations.

    PubMed

    Palmer, Michael H; Ridley, Trevor; Hoffmann, Søren Vrønning; Jones, Nykola C; Coreno, Marcello; de Simone, Monica; Grazioli, Cesare; Zhang, Teng; Biczysko, Malgorzata; Baiardi, Alberto; Peterson, Kirk

    2015-10-28

    New photoelectron, ultraviolet (UV), and vacuum UV (VUV) spectra have been obtained for bromobenzene by synchrotron study with higher sensitivity and resolution than previous work. This, together with use of ab initio calculations with both configuration interaction and time dependent density functional theoretical methods, has led to major advances in interpretation. The VUV spectrum has led to identification of a considerable number of Rydberg states for the first time. The Franck-Condon (FC) analyses including both hot and cold bands lead to identification of the vibrational structure of both ionic and electronically excited states including two Rydberg states. The UV onset has been interpreted in some detail, and an interpretation based on the superposition of FC and Herzberg-Teller contributions has been performed. In a similar way, the 6 eV absorption band which is poorly resolved is analysed in terms of the presence of two ππ* states of (1)A1 (higher oscillator strength) and (1)B2 (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2(2)B1 ionic state is particularly challenging, and the best interpretation is based on equation-of-motion-coupled cluster with singles and doubles computations. A number of equilibrium structures of the ionic and singlet excited states show that the molecular structure is less subject to variation than corresponding studies for iodobenzene. The equilibrium structures of the 3b13s and 6b23s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures.

  19. Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations

    SciTech Connect

    Palmer, Michael H. Ridley, Trevor E-mail: vronning@phys.au.dk E-mail: marcello.coreno@elettra.eu E-mail: malgorzata.biczysko@sns.it; Hoffmann, Søren Vrønning E-mail: vronning@phys.au.dk E-mail: marcello.coreno@elettra.eu E-mail: malgorzata.biczysko@sns.it Jones, Nykola C. E-mail: vronning@phys.au.dk E-mail: marcello.coreno@elettra.eu E-mail: malgorzata.biczysko@sns.it; Coreno, Marcello E-mail: vronning@phys.au.dk E-mail: marcello.coreno@elettra.eu E-mail: malgorzata.biczysko@sns.it; Grazioli, Cesare; Zhang, Teng; and others

    2015-10-28

    New photoelectron, ultraviolet (UV), and vacuum UV (VUV) spectra have been obtained for bromobenzene by synchrotron study with higher sensitivity and resolution than previous work. This, together with use of ab initio calculations with both configuration interaction and time dependent density functional theoretical methods, has led to major advances in interpretation. The VUV spectrum has led to identification of a considerable number of Rydberg states for the first time. The Franck-Condon (FC) analyses including both hot and cold bands lead to identification of the vibrational structure of both ionic and electronically excited states including two Rydberg states. The UV onset has been interpreted in some detail, and an interpretation based on the superposition of FC and Herzberg-Teller contributions has been performed. In a similar way, the 6 eV absorption band which is poorly resolved is analysed in terms of the presence of two ππ* states of {sup 1}A{sub 1} (higher oscillator strength) and {sup 1}B{sub 2} (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2{sup 2}B{sub 1} ionic state is particularly challenging, and the best interpretation is based on equation-of-motion-coupled cluster with singles and doubles computations. A number of equilibrium structures of the ionic and singlet excited states show that the molecular structure is less subject to variation than corresponding studies for iodobenzene. The equilibrium structures of the 3b{sub 1}3s and 6b{sub 2}3s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures.

  20. Electronic structure and spectroscopy of nucleic acid bases: Ionization energies, ionization-induced structural changes, and photoelectron spectra

    SciTech Connect

    Bravaya, Ksenia B.; Kostko, Oleg; Dolgikh, Stanislav; Landau, Arie; Ahmed, Musahid; Krylov, Anna I.

    2010-08-02

    We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed using equation-of-motion coupled-cluster method for ionization potentials with single and double substitutions. Equilibrium structures of the cationic ground states were characterized by DFT with the {omega}B97X-D functional. The ionization-induced geometry changes of the bases are consistent with the shapes of the corresponding molecular orbitals. For the lowest-energy tautomers, the magnitude of the structural relaxation decreases in the following series G > C > A > T, the respective relaxation energies being 0.41, 0.32, 0.25 and 0.20 eV. The computed adiabatic ionization energies (8.13, 8.89, 8.51-8.67 and 7.75-7.87 eV for A,T,C and G, respectively) agree well with the onsets of the photoionization efficiency (PIE) curves (8.20 {+-} 0.05, 8.95 {+-} 0.05, 8.60 {+-} 0.05 and 7.75 {+-} 0.05 eV). Vibrational progressions for the S{sub 0}-D{sub 0} vibronic bands computed within double-harmonic approximation with Duschinsky rotations are compared with previously reported experimental photoelectron spectra.

  1. Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations.

    PubMed

    Palmer, Michael H; Ridley, Trevor; Hoffmann, Søren Vrønning; Jones, Nykola C; Coreno, Marcello; de Simone, Monica; Grazioli, Cesare; Zhang, Teng; Biczysko, Malgorzata; Baiardi, Alberto; Peterson, Kirk

    2015-10-28

    New photoelectron, ultraviolet (UV), and vacuum UV (VUV) spectra have been obtained for bromobenzene by synchrotron study with higher sensitivity and resolution than previous work. This, together with use of ab initio calculations with both configuration interaction and time dependent density functional theoretical methods, has led to major advances in interpretation. The VUV spectrum has led to identification of a considerable number of Rydberg states for the first time. The Franck-Condon (FC) analyses including both hot and cold bands lead to identification of the vibrational structure of both ionic and electronically excited states including two Rydberg states. The UV onset has been interpreted in some detail, and an interpretation based on the superposition of FC and Herzberg-Teller contributions has been performed. In a similar way, the 6 eV absorption band which is poorly resolved is analysed in terms of the presence of two ππ* states of (1)A1 (higher oscillator strength) and (1)B2 (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2(2)B1 ionic state is particularly challenging, and the best interpretation is based on equation-of-motion-coupled cluster with singles and doubles computations. A number of equilibrium structures of the ionic and singlet excited states show that the molecular structure is less subject to variation than corresponding studies for iodobenzene. The equilibrium structures of the 3b13s and 6b23s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures. PMID:26520509

  2. Correlations Between Variations in Solar EUV and Soft X-Ray Irradiance and Photoelectron Energy Spectra Observed on Mars and Earth

    NASA Technical Reports Server (NTRS)

    Peterson, W. K.; Brain, D. A.; Mitchell, D. L.; Bailey, S. M.; Chamberlin, P. C.

    2013-01-01

    Solar extreme ultraviolet (EUV; 10-120 nm) and soft X-ray (XUV; 0-10 nm) radiation are major heat sources for the Mars thermosphere as well as the primary source of ionization that creates the ionosphere. In investigations of Mars thermospheric chemistry and dynamics, solar irradiance models are used to account for variations in this radiation. Because of limited proxies, irradiance models do a poor job of tracking the significant variations in irradiance intensity in the EUV and XUV ranges over solar rotation time scales when the Mars-Sun-Earth angle is large. Recent results from Earth observations show that variations in photoelectron energy spectra are useful monitors of EUV and XUV irradiance variability. Here we investigate photoelectron energy spectra observed by the Mars Global Surveyor (MGS) Electron Reflectometer (ER) and the FAST satellite during the interval in 2005 when Earth, Mars, and the Sun were aligned. The Earth photoelectron data in selected bands correlate well with calculations based on 1 nm resolution observations above 27 nm supplemented by broadband observations and a solar model in the 0-27 nm range. At Mars, we find that instrumental and orbital limitations to the identifications of photoelectron energy spectra in MGS/ER data preclude their use as a monitor of solar EUV and XUV variability. However, observations with higher temporal and energy resolution obtained at lower altitudes on Mars might allow the separation of the solar wind and ionospheric components of electron energy spectra so that they could be used as reliable monitors of variations in solar EUV and XUV irradiance than the time shifted, Earth-based, F(10.7) index currently used.

  3. XPS and bioactivity study of the bisphosphonate pamidronate adsorbed onto plasma sprayed hydroxyapatite coatings

    NASA Astrophysics Data System (ADS)

    McLeod, Kate; Kumar, Sunil; Smart, Roger St. C.; Dutta, Naba; Voelcker, Nicolas H.; Anderson, Gail I.; Sekel, Ron

    2006-12-01

    This paper reports the use of X-ray photoelectron spectroscopy (XPS) to investigate bisphosphonate (BP) adsorption onto plasma sprayed hydroxyapatite (HA) coatings commonly used for orthopaedic implants. BPs exhibit high binding affinity for the calcium present in HA and hence can be adsorbed onto HA-coated implants to exploit their beneficial properties for improved bone growth at the implant interface. A rigorous XPS analysis of pamidronate, a commonly used nitrogenous BP, adsorbed onto plasma sprayed HA-coated cobalt-chromium substrates has been carried out, aimed at: (a) confirming the adsorption of this BP onto HA; (b) studying the BP diffusion profile in the HA coating by employing the technique of XPS depth profiling; (c) confirming the bioactivity of the adsorbed BP. XPS spectra of plasma sprayed HA-coated discs exposed to a 10 mM aqueous BP solution (pamidronate) for periods of 1, 2 and 24 h showed nitrogen and phosphorous photoelectron signals corresponding to the BP, confirming its adsorption onto the HA substrate. XPS depth profiling of the 2 h BP-exposed HA discs showed penetration of the BP into the HA matrix to depths of at least 260 nm. The bioactivity of the adsorbed BP was confirmed by the observed inhibition of osteoclast (bone resorbing) cell activity. In comparison to the HA sample, the HA sample with adsorbed BP exhibited a 25-fold decrease in primary osteoclast cells.

  4. Fingerprints of the hydrogen bond in the photoemission spectra of croconic acid condensed phase: An x-ray photoelectron spectroscopy and ab-initio study

    SciTech Connect

    Bisti, F.; Stroppa, A.; Picozzi, S.; Ottaviano, L.

    2011-05-07

    The electronic structure of Croconic Acid in the condensed phase has been studied by comparing core level and valence band x-ray photoelectron spectroscopy experiments and first principles density functional theory calculations using the Heyd-Scuseria-Ernzerhof screened hybrid functional and the GW approximation. By exploring the photoemission spectra for different deposition thicknesses, we show how the formation of the hydrogen bond network modifies the O 1s core level lineshape. Moreover, the valence band can be explained only if the intermolecular interactions are taken into account in the theoretical approach.

  5. Size- and intensity-dependent photoelectron spectra from gas-phase gold nanoparticles irradiated by intense femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Powell, J.; Robatjazi, S. J.; Makhija, V.; Vajdi, A.; Li, X.; Malakar, Y.; Pearson, W. L.; Rudenko, A.; Sorensen, C.; Stierle, J.; Kling, M. F.

    2016-05-01

    Nanoparticles bridge the gap between atomic/molecular and bulk matter offering unique opportunities to study light interactions with complex systems, in particular, near-field enhancements and excitation of plasmons. Here we report on a systematic study of photoelectron emission from isolated gold nanoparticles irradiated by 800 nm, 25 fs laser pulses at 10-50 TW/ cm2 peak intensities. A combination of an aerodynamic lens nanoparticle injector, high-energy velocity-map imaging spectrometer and a high-speed, single-shot camera is employed to record shot by shot photoelectron emission patterns from individual particles. By sorting the recorded images according to the number of emitted electrons, we select the events from the regions of particular laser intensities within the laser focus, thus, essentially avoiding focal volume averaging. Using this approach, we study the intensity- and size-dependence of photoelectron energy and angular distributions for particle sizes ranging from 5 nm to 400 nm. This work is supported by NSF Award No. IIA-143049. JRML operations and personal are supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of BES, Office of Science, U. S. DOE.

  6. Photoelectron spectra and structures of three cyclic dipeptides: PhePhe, TyrPro, and HisGly

    NASA Astrophysics Data System (ADS)

    Wickrama Arachchilage, Anoja P.; Wang, Feng; Feyer, Vitaliy; Plekan, Oksana; Prince, Kevin C.

    2012-03-01

    We have investigated the electronic structure of three cyclic dipeptides: cyclo(Histidyl-Glycyl) (cHisGly), cyclo(Tyrosyl-Prolyl) (cTyrPro), and cyclo(Phenylalanyl-Phenylalanyl) (cPhePhe) in the vapor phase, by means of photoemission spectroscopy and theoretical modeling. The last compound was evaporated from the solid linear dipeptide, but cyclised, losing water to form cPhePhe in the gas phase. The results are compared with our previous studies of three other cyclopeptides. Experimental valence and core level spectra have been interpreted in the light of calculations to identify the basic chemical properties associated with the central diketopiperazine ring, and with the additional functional groups. The valence spectra are generally characterized by a restricted set of outer valence orbitals separated by a gap from most other valence orbitals. The theoretically simulated core and valence spectra of all three cyclic dipeptides agree reasonably well with the experimental spectra. The central ring and the side chains act as independent chromophores whose spectra do not influence one another, except for prolyl dipeptides, where the pyrrole ring is fused with the central ring. In this case, significant changes in the valence and core level spectra were observed, and explained by stronger hybridization of the valence orbitals.

  7. A theoretical study on the lonic states and the photoelectron spectra of dichlorodifluoromethane (CF 2Cl 2)

    NASA Astrophysics Data System (ADS)

    Takeshita, Kouichi

    1990-07-01

    Ab initio calculations are performed to study the molecular equilibrium structure and the harmonic vibrational frequency of the low-lying four ionic states 2B2, 2A2, 2B1, and 2A1 of dichlorodifluoromethane (CF 2Cl 2). The theoretical intensity curve obtained from the Franck-Condon factors is in good agreement with the photoelectron, (PE) spectrum. The results show that the four maxima of the PE spectrum from the lower energy side correspond to the 2B2, 2A2, 2B1, and 2A1 states. Three vibrational progressions are found in the theoretical intensity curve of 2B2. Higher vibrational excitations to the ν4 (ClCCl bending) mode contribute to all progressions and vibrational excitations of the ν1 and ν3 modes also contribute to intensity.

  8. Photoelectron Spectroscopy of U Oxide at LLNL

    SciTech Connect

    Tobin, J G; Yu, S; Chung, B W; Waddill, G D

    2010-03-02

    In our laboratory at LLNL, an effort is underway to investigate the underlying complexity of 5f electronic structure with spin-resolved photoelectron spectroscopy using chiral photonic excitation, i.e. Fano Spectroscopy. Our previous Fano measurements with Ce indicate the efficacy of this approach and theoretical calculations and spectral simulations suggest that Fano Spectroscopy may resolve the controversy concerning Pu electronic structure and electron correlation. To this end, we have constructed and commissioned a new Fano Spectrometer, testing it with the relativistic 5d system Pt. Here, our preliminary photoelectron spectra of the UO{sub 2} system are presented. X-ray photoelectron spectroscopy has been used to characterize a sample of UO{sub 2} grown on an underlying substrate of Uranium. Both AlK{alpha} (1487 eV) and MgK{alpha} (1254 eV) emission were utilized as the excitation. Using XPS and comparing to reference spectra, it has been shown that our sample is clearly UO{sub 2}.

  9. XPS Study of Plasma- and Argon Ion-Sputtered Polytetrafluoroethylene

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Kliss, Mark (Technical Monitor)

    1997-01-01

    The similarity of plasma-polymerized tetrafluoroethylene (PPTFE) and the fluoropolymer film deposited by rf (radio frequency) plasma sputtering (SPTFE) of polytetrafluoroethylene (PTFE), noted earlier in the literature, has been reconfirmed. FT-IR (Fourier Transform Infrared), XPS (X ray Photoelectron Spectroscopy) and UV (ultraviolet) spectroscopy has been employed in apparently the first study to involve preparation of PPTFE and SPTFE in the same reactor and under comparable low-power plasma conditions. Most of the work concerned the use of He or Ar as sputtering gas, but some runs were also carried out with the other rare gases Ne, Kr and Xe. The C1s XPS spectra of SPTFE films displayed a relatively higher content of CF2 groups, and yielded higher F/C (fluorine / carbon) ratios, than PPTFE films, while the SPTFE films were somewhat more transparent in the UV than PPTFE. The F/C ratios for SPTFE were essentially independent of the rare gas used for sputtering. Increasing rf power from 10 to 50 W for Xe plasma-sputtering of PTFE resulted in successively lower F/C ratios (1.55 to 1.21), accompanied by sputtering of the glass reactor occurring at 40 W and above. Some limited XPS, FT-IR and UV data are presented on Ar ion-sputtered PTFE.

  10. The Role of Spin-Orbit Coupling in the Double-Ionization Photoelectron Spectra of XCN(2+) (X = Cl, Br, and I).

    PubMed

    Manna, Soumitra; Mishra, Sabyashachi

    2016-03-10

    The photoelectron spectra of XCN(2+) (X = Cl, Br, and I) were calculated employing ab initio electronic structure methods with high-level electron correlation and explicit treatment of spin-orbit coupling. Twelve scalar-relativistic excited states of the dicationic systems, calculated from state-averaged CASSCF/MRCI calculations, were used as the electronic basis to evaluate spin-orbit eigenstates. While the spin-orbit effects in ClCN(2+) are found to be negligible, the electronic spectroscopy of BrCN(2+) and ICN(2+) is significantly influenced by interstate spin-orbit coupling. Several electronic degeneracies are lifted, and many unexpected accidental degeneracies occurred due to the spin-orbit coupling. In particular, the spin-orbit interactions between X̃ (3)Σ(-)-b̃ (1)Σ(+), Ã (3)Π-c̃ (1)Π, B̃ (3)Δ-ã (1)Δ, and C̃ (3)Σ(+)-d̃ (1)Σ(-) are found to be strong in BrCN(2+) and ICN(2+). By careful analysis of the effect of spin-orbit coupling parameters and the spin-orbit eigenstate composition, an assignment of the hitherto unidentified experimental photoelectron bands of BrCN(2+) and ICN(2+) is presented.

  11. Electronic structure of metal clusters. 4. Photoelectron spectra and molecular orbital calculations on cobalt, iron, ruthenium, and osmium sulfide nonacarbonyl clusters

    SciTech Connect

    Chesky, P.T.; Hall, M.B.

    1983-10-01

    Gas-phase, ultraviolet photoelectron (PE) spectra and molecular orbital (MO) calculations are reported for SCo/sub 3/(CO)/sub 9/, SH/sub n-//sub 1/Fe/sub n/Co/sub 3//sub -n/(CO)/sub 9/ (n = 1-3), S/sub 2/Fe/sub 3/(CO)/sub 9/, and SH/sub 2/M/sub 3/(CO)/sub 9/ (M = Fe, Ru, Os). The first PE spectra reported for mixed-metal clusters are included in this series. As Co atoms are replaced by the isoelectronic FeH unit, the spectra show the loss of a Co band and the appearance of an Fe band. This phenomenon suggests that the d bands localize upon ionization. In a comparison with the PE spectrum of M/sub 3/(CO)/sub 12/ (M = Fe, Ru, Os), the major spectral changes for SH/sub 2/M/sub 3/(CO)/sub 9/ (M = Fe, Ru, Os) are the loss of a band corresponding to direct M-M interactions and the appearance of bands due to a mixture of energy-equivalent M-H-M and M-S interactions. The spectra also show a substantial rearrangement of the bands due to the t/sub 2g/-like electrons, which are usually considered M-CO ..pi.. bonding. An antibonding interaction between a S orbital and the t/sub 2g/-like orbitals is responsible for a unique band in the spectra which occurs at high ionization energy between the M-M bonding band and the main t/sub 2//sub g/-like band. 12 figures, 9 tables

  12. Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions

    NASA Astrophysics Data System (ADS)

    Olivieri, Giorgia; Parry, Krista M.; Powell, Cedric J.; Tobias, Douglas J.; Brown, Matthew A.

    2016-04-01

    Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy (XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyte interface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquid interface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.

  13. Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions.

    PubMed

    Olivieri, Giorgia; Parry, Krista M; Powell, Cedric J; Tobias, Douglas J; Brown, Matthew A

    2016-04-21

    Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy(XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyteinterface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt to provide a complete description of the liquidinterface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here, we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30% between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic-scattering events at low photoelectron kinetic energies (<300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquidinterfaces are discussed. PMID:27389231

  14. The vacuum-ultraviolet photoelectron spectra of CH2F2 and CH2Cl2 revisited

    NASA Astrophysics Data System (ADS)

    Tuckett, Richard; Harvey, Jonelle; Hemberger, Patrick; Bodi, Andras

    2015-09-01

    The threshold photoelectron spectrum (TPES) of difluoromethane and dichloromethane has been recorded at the Swiss Light Source with a resolution of 2 meV or 16 cm-1. Electronic and vibronic transitions are simulated and assigned with the help of Franck-Condon (FC) calculations based on coupled cluster electronic structure calculations for the equilibrium geometries and harmonic vibrational frequencies of the neutrals, and of the ground and excited electronic states of the cations. Notwithstanding a high-resolution pulsed-field ionisation study on CH2F2 (Forysinski et al., 2010) in which a number of transitions to the X∼+ state have been recorded with unprecedented accuracy, we report the first complete vibrationally resolved overview of the low-lying electronic states of CH2X2+, X = F or Cl. Hydrogen atom loss from CH2F2+ occurs at low energy, making the ground state rather anharmonic and interpretation of the X∼+ band challenging in the harmonic approximation. By Franck-Condon fits, the adiabatic ionisation energies to the A∼+ 2B2, C∼+ 2A2 and D∼+ 2B2 states have been determined as 14.3 ± 0.1, 15.57 ± 0.01 and 18.0 ± 0.1 eV, respectively. The first band in the CH2Cl2 TPES is complex for a different reason, as it is the result of two overlapping ionic states, X∼+ 2B2 and A∼+ 2B1, with derived ionisation energies of 11.0 ± 0.2 and 11.317 ± 0.006 eV, and dominated by an extended progression in the CCl2 bend (in X∼+) and a short progression in the CCl2 symmetric stretch (in A∼+), respectively. Furthermore, even though Koopmans' approximation holds for the vertical ionisations, the X∼+ state of CH2Cl2+ is stabilized by geometry relaxation and corresponds to ionisation from the (HOMO-1) orbital. That is, the first two vertical ionisation energies are in the same order as the negative of the orbital energies of the highest occupied orbitals, but the adiabatic ionisation energy corresponding to electron removal from the (HOMO-1) is lower than the

  15. Are carboxyl groups the most acidic sites in amino acids? Gas-phase acidities, photoelectron spectra, and computations on tyrosine, p-hydroxybenzoic acid, and their conjugate bases.

    PubMed

    Tian, Zhixin; Wang, Xue-Bin; Wang, Lai-Sheng; Kass, Steven R

    2009-01-28

    Deprotonation of tyrosine in the gas phase was found to occur preferentially at the phenolic site, and the conjugate base consists of a 70:30 mixture of phenoxide and carboxylate anions at equilibrium. This result was established by developing a chemical probe for differentiating these two isomers, and the presence of both ions was confirmed by photoelectron spectroscopy. Equilibrium acidity measurements on tyrosine indicated that deltaG(acid)(o) = 332.5 +/- 1.5 kcal mol(-1) and deltaH(acid)(o) = 340.7 +/- 1.5 kcal mol(-1). Photoelectron spectra yielded adiabatic electron detachment energies of 2.70 +/- 0.05 and 3.55 +/- 0.10 eV for the phenoxide and carboxylate anions, respectively. The H/D exchange behavior of deprotonated tyrosine was examined using three different alcohols (CF3CH2OD, C6H5CH2OD, and CH3CH2OD), and incorporation of up to three deuterium atoms was observed. Two pathways are proposed to account for these results, and all of the experimental findings are supplemented with B3LYP/aug-cc-pVDZ and G3B3 calculations. In addition, it was found that electrospray ionization of tyrosine from a 3:1 (v/v) CH3OH/H2O solution using a commercial source produces a deprotonated [M-H]- anion with the gas-phase equilibrium composition rather than the structure of the ion that exists in aqueous media. Electrospray ionization from acetonitrile, however, leads largely to the liquid-phase (carboxylate) structure. A control molecule, p-hydroxybenzoic acid, was found to behave in a similar manner. Thus, the electrospray conditions that are employed for the analysis of a compound can alter the isomeric composition of the resulting anion.

  16. From photoelectron detachment spectra of BrHBr(-), BrDBr(-) and IHI(-), IDI(-) to vibrational bonding of BrMuBr and IMuI.

    PubMed

    Manz, Jörn; Sato, Kazuma; Takayanagi, Toshiyuki; Yoshida, Takahiko

    2015-04-28

    Photoelectron detachment XLX(-)(00(0)0) + hν → XLX(vib) + e(-) + KER (X = Br or I, L = H or D) at sufficiently low temperatures photoionizes linear dihalogen anions XLX(-) in the vibrational ground state (v1v2 (l)v3 = 00(0)0) and prepares the neutral radicals XLX(vib) in vibrational states (vib). At the same time, part of the photon energy (hν) is converted into kinetic energy release (KER) of the electron [R. B. Metz, S. E. Bradforth, and D. M. Neumark, Adv. Chem. Phys. 81, 1 (1992)]. The process may be described approximately in terms of a Franck-Condon type transfer of the vibrational wavefunction representing XLX(-)(00(0)0) from the domain close to the minimum of its potential energy surface (PES) to the domain close to the linear transition state of the PES of the neutral XLX. As a consequence, prominent peaks of the photoelectron detachment spectra (pds) correlate with the vibrational energies EXLX,vib of states XLX(vib) which are centered at linear transition state. The corresponding vibrational quantum numbers may be labeled vib = (v1v2 (l)v3) = (00(0)v3). Accordingly, the related most prominent peaks in the pds are labeled v3. We construct a model PES which mimics the "true" PES in the domain of transition state such that it supports vibrational states with energies EXLX,pds,00(0)v3 close to the peaks of the pds labeled v3 = 0, 2, and 4. Subsequently, the same model PES is also used to calculate approximate values of the energies EXMuX,00(0)0 of the isotopomers XMuX(00(0)0). For the heavy isotopomers XHX and XDX, it turns out that all energies EXLX,00(0)v3 are above the threshold for dissociation, which means that all heavy XLX(00(0)v3) with wavefunctions centered at the transition state are unstable resonances with finite lifetimes. Turning the table, bound states of the heavy XLX are van der Waals (vdW) bonded. In contrast, the energies EXMuX,00(0)0 of the light isotopomers XMuX(00(0)0) are below the threshold for dissociation, with wavefunctions

  17. From photoelectron detachment spectra of BrHBr-, BrDBr- and IHI-, IDI- to vibrational bonding of BrMuBr and IMuI

    NASA Astrophysics Data System (ADS)

    Manz, Jörn; Sato, Kazuma; Takayanagi, Toshiyuki; Yoshida, Takahiko

    2015-04-01

    Photoelectron detachment XLX-(0000) + hν → XLX(vib) + e- + KER (X = Br or I, L = H or D) at sufficiently low temperatures photoionizes linear dihalogen anions XLX- in the vibrational ground state (v1v2lv3 = 0000) and prepares the neutral radicals XLX(vib) in vibrational states (vib). At the same time, part of the photon energy (hν) is converted into kinetic energy release (KER) of the electron [R. B. Metz, S. E. Bradforth, and D. M. Neumark, Adv. Chem. Phys. 81, 1 (1992)]. The process may be described approximately in terms of a Franck-Condon type transfer of the vibrational wavefunction representing XLX-(0000) from the domain close to the minimum of its potential energy surface (PES) to the domain close to the linear transition state of the PES of the neutral XLX. As a consequence, prominent peaks of the photoelectron detachment spectra (pds) correlate with the vibrational energies EXLX,vib of states XLX(vib) which are centered at linear transition state. The corresponding vibrational quantum numbers may be labeled vib = (v1v2lv3) = (000v3). Accordingly, the related most prominent peaks in the pds are labeled v3. We construct a model PES which mimics the "true" PES in the domain of transition state such that it supports vibrational states with energies EXLX,pds,000v3 close to the peaks of the pds labeled v3 = 0, 2, and 4. Subsequently, the same model PES is also used to calculate approximate values of the energies EXMuX,0000 of the isotopomers XMuX(0000). For the heavy isotopomers XHX and XDX, it turns out that all energies EXLX,000v3 are above the threshold for dissociation, which means that all heavy XLX(000v3) with wavefunctions centered at the transition state are unstable resonances with finite lifetimes. Turning the table, bound states of the heavy XLX are van der Waals (vdW) bonded. In contrast, the energies EXMuX,0000 of the light isotopomers XMuX(0000) are below the threshold for dissociation, with wavefunctions centered at the transition state. This

  18. Surface characterization of coated powders with XPS: Al2O3-SiO2 coated TiO2 pigments

    NASA Astrophysics Data System (ADS)

    Johansson, Leena-Sisko; Losoi, Tuomo

    A study aimed at finding experimental strategies to characterize surface structures of coated powders with X-ray Photoelectron Spectroscopy (XPS) was reported. As an example, industrial TiO2 pigments, coated with hydrous alumina and silica were studied using different XPS methods. Isoeletric points and x-ray fluorescence analyses were also measured for comparison. The applicability of an XPS analysis method introduced by Tougaard et al was studied. In the method, the depth an element is calculated, analyzing elastic and inelastic photoelectron emissions from a low resolution XPS spectra. Used together with conventional analysis, two independent analyses may be calculated from line low resolution XPS spectrum. For fast and simple analysis, peak to background ratio D for the element can be measured. Good correlation was found between the results from conventional XPS layer calculations and the Tougaard equation. The methods are independent of each other. Together they seemed to give more reliable information on the nonideal powder surfaces studied than either of the methods alone.

  19. A comparative study on defect estimation using XPS and Raman spectroscopy in few layer nanographitic structures.

    PubMed

    Ganesan, K; Ghosh, Subrata; Gopala Krishna, Nanda; Ilango, S; Kamruddin, M; Tyagi, A K

    2016-08-10

    Defects in planar and vertically oriented nanographitic structures (NGSs) synthesized by plasma enhanced chemical vapor deposition (PECVD) have been investigated using Raman and X-ray photoelectron spectroscopy. While Raman spectra reveal the dominance of vacancy and boundary type defects respectively in vertical and planar NGSs, XPS provides additional information on vacancy related defect peaks in the C 1s spectrum, which originate from non-conjugated carbon atoms in the hexagonal lattice. Although an excellent correlation prevails between these two techniques, our results show that estimation of surface defects by XPS is more accurate than Raman analysis. Nuances of these techniques are discussed in the context of assessing defects in nanographitic structures. PMID:27445041

  20. Valence band structure of binary chalcogenide vitreous semiconductors by high-resolution XPS

    SciTech Connect

    Kozyukhin, S.; Golovchak, R.; Kovalskiy, A.; Shpotyuk, O.; Jain, H.

    2011-04-15

    High-resolution X-ray photoelectron spectroscopy (XPS) is used to study regularities in the formation of valence band electronic structure in binary As{sub x}Se{sub 100-x}, As{sub x}S{sub 100-x}, Ge{sub x}Se{sub 100-x} and Ge{sub x}S{sub 100-x} chalcogenide vitreous semiconductors. It is shown that the highest occupied energetic states in the valence band of these materials are formed by lone pair electrons of chalcogen atoms, which play dominant role in the formation of valence band electronic structure of chalcogen-rich glasses. A well-expressed contribution from chalcogen bonding p electrons and more deep s orbitals are also recorded in the experimental valence band XPS spectra. Compositional dependences of the observed bands are qualitatively analyzed from structural and compositional points of view.

  1. Rotationally resolved vibrational spectra of AsH3 (+)X̃(2)A2 (″): Tunneling splittings studied by zero-kinetic-energy photoelectron spectroscopy.

    PubMed

    Sun, Wei; Dai, Zuyang; Wang, Jia; Mo, Yuxiang

    2016-06-21

    The rotationally resolved vibrational spectra of AsH3 (+)X̃(2)A2 (″) have been measured for the first time with vibrational energies up to 6000 cm(-1) above the ground state using the zero-kinetic-energy photoelectron method. The symmetric inversion vibrational energy levels (v2 (+)) and the corresponding rotational constants for v2 (+)=0-15 have been determined. The tunneling splittings of the inversion vibration energy levels have been observed and are 0.8 and 37.7 (±0.5) cm(-1) for the ground and the first excited vibrational states, respectively. The first adiabatic ionization energy for AsH3 was determined as 79 243.3 ± 1 cm(-1). The geometric parameters of AsH3 (+)X̃(2)A2 (″) as a function of inversion vibrational numbers have been determined, indicating that the geometric structure of the cation changes from near-planar to pyramidal with increasing inversion vibrational excitation. In addition to the experimental measurements, a two-dimensional theoretical calculation considering the two symmetric vibrational modes was performed to determine the energy levels of the symmetric inversion, which are in good agreement with the experimental results. The inversion vibrational energy levels of SbH3 (+)X̃(2)A2 (″) have also been calculated and are found to have much smaller energy splittings than those of AsH3 (+)X̃(2)A2 (″).

  2. Rotationally resolved vibrational spectra of AsH3 + (" separators=" X ˜ 2 A2 ″) : Tunneling splittings studied by zero-kinetic-energy photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, Wei; Dai, Zuyang; Wang, Jia; Mo, Yuxiang

    2016-06-01

    The rotationally resolved vibrational spectra of AsH3 + (" separators=" X ˜ 2 A2 ″) have been measured for the first time with vibrational energies up to 6000 cm-1 above the ground state using the zero-kinetic-energy photoelectron method. The symmetric inversion vibrational energy levels ( v2 +) and the corresponding rotational constants for v2 + = 0 -15 have been determined. The tunneling splittings of the inversion vibration energy levels have been observed and are 0.8 and 37.7 (±0.5) cm-1 for the ground and the first excited vibrational states, respectively. The first adiabatic ionization energy for AsH3 was determined as 79 243.3 ± 1 cm-1. The geometric parameters of AsH3 + (" separators=" X ˜ 2 A2 ″) as a function of inversion vibrational numbers have been determined, indicating that the geometric structure of the cation changes from near-planar to pyramidal with increasing inversion vibrational excitation. In addition to the experimental measurements, a two-dimensional theoretical calculation considering the two symmetric vibrational modes was performed to determine the energy levels of the symmetric inversion, which are in good agreement with the experimental results. The inversion vibrational energy levels of SbH3 + (" separators=" X ˜ 2 A2 ″) have also been calculated and are found to have much smaller energy splittings than those of AsH3 + (" separators=" X ˜ 2 A2 ″) .

  3. Theoretical studies on the electronic structures and photoelectron spectra of tri-rhenium oxide clusters: Re3On- and Re3On (n = 1-6)

    NASA Astrophysics Data System (ADS)

    Zhou, Qi; Gong, Wei-Chao; Xie, Lu; Zheng, Cun-Gong; Zhang, Wei; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-01-01

    Density functional theory (DFT) calculations are performed to study the structural and electronic properties of tri-rhenium oxide clusters Re3On-/0 (n = 1-6). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level are carried out to search for the global minima for both the anions and the neutrals. For the anions, the first two O atoms prefer the same corner position of a Re3 triangle. Whereas, Re3O3- possesses a C2v symmetry with one bridging and two terminal O atoms. The next three O atoms (n = 4-6) are adding sequentially on the basis of Re3O3- motif, i.e., adding one terminal O atom for Re3O4-, one terminal and one bridging O atoms for Re3O5-, and one terminal and two bridging O atoms for Re3O6-, respectively. Their corresponding neutral species are similar to the anions in geometry except Re3O4 and Re3O5. Molecular orbital analyses are employed to investigate the chemical bonding and structural evolution in these tri-rhenium oxide clusters.

  4. Energy Thresholds of DNA Damage Induced by UV Radiation: An XPS Study.

    PubMed

    Gomes, P J; Ferraria, A M; Botelho do Rego, A M; Hoffmann, S V; Ribeiro, P A; Raposo, M

    2015-04-30

    This work stresses on damage at the molecular level caused by ultraviolet radiation (UV) in the range from 3.5 to 8 eV, deoxyribonucleic acid (DNA) films observed by X-ray photoelectron spectroscopy (XPS). Detailed quantitative XPS analysis, in which all the amounts are relative to sodium-assumed not to be released from the samples, of the carbon, oxygen, and particularly, nitrogen components, reveals that irradiation leads to sugar degradation with CO-based compounds release for energies above 6.9 eV and decrease of nitrogen groups which are not involved in hydrogen bonding at energies above 4.2 eV. Also the phosphate groups are seen to decrease to energies above 4.2 eV. Analysis of XPS spectra allowed to conclude that the damage on bases peripheral nitrogen atoms are following the damage on phosphates. It suggests that very low kinetic energy photoelectrons are ejected from the DNA bases, as a result of UV light induced breaking of the phosphate ester groups which forms a transient anion with resonance formation and whereby most of the nitrogen DNA peripheral groups are removed. The degree of ionization of DNA was observed to increase with radiation energy, indicating that the ionized phosphate groups are kept unchanged. This result was interpreted by the shielding of phosphate groups caused by water molecules hydration near sodium atoms. PMID:25844940

  5. A photoelectron spectroscopy study of the electronic structure evolution in CuInSe{sub 2}-related compounds at changing copper content

    SciTech Connect

    Kuznetsova, T. V.; Grebennikov, V. I.; Zhao, H.; Derks, C.; Taubitz, C.; Neumann, M.; Persson, C.; Kuznetsov, M. V.; Bodnar, I. V.; Martin, R. W.; Yakushev, M. V.

    2012-09-10

    Evolution of the valence-band structure at gradually increasing copper content has been analysed by x-ray photoelectron spectroscopy (XPS) in In{sub 2}Se{sub 3}, CuIn{sub 5}Se{sub 8}, CuIn{sub 3}Se{sub 5}, and CuInSe{sub 2} single crystals. A comparison of these spectra with calculated total and angular-momentum resolved density-of-states (DOS) revealed the main trends of this evolution. The formation of the theoretically predicted gap between the bonding and non-bonding states has been observed in both experimental XPS spectra and theoretical DOS.

  6. Relating the 4s{sigma}{sup -1} inner-valence photoelectron spectrum of HBr with the Br 3d{sup -1}5l{lambda} resonant Auger spectra: An approach to the assignments

    SciTech Connect

    Puettner, R.; Hu, Y. F.; Bancroft, G. M.; Kivimaeki, A.; Jurvansuu, M.; Aksela, H.; Aksela, S.

    2003-09-01

    The high resolution Br 4s{sigma}{sup -1} photoelectron spectrum of HBr is presented together with the resonant Auger spectra resulting from excitations from the 3d core levels to the low-n Rydberg orbitals 5s{sigma}, 5p{sigma}, and 5p{pi}. The very complex spectra can be broadly assigned using two observations. First, the energy splittings of the 4p{pi}{sup -2}5s and 4p{pi}{sup -2}5p states are very similar to the splittings of the 4p{pi}{sup -2}({sup 1}{sigma}{sup +},{sup 1}{delta}, and {sup 3}{sigma}{sup -}) final states seen previously in the normal Auger spectra. Second, the {sup 2}{sigma}{sup +} states, which are the dominant correlation satellites in the complex 4s{sigma}{sup -1} photoelectron spectrum, are often enhanced in the 5s{sigma} resonance Auger spectra. Electron correlation and spin-orbit interaction in the final states are important to understand all of these spectra. Unlike the normal Auger spectra, vibrational excitations play only a minor role in these spectra, showing that the 5s and 5p Rydberg orbitals have some bonding character.

  7. X-ray Photoelectron Spectroscopy Database (Version 4.1)

    National Institute of Standards and Technology Data Gateway

    SRD 20 X-ray Photoelectron Spectroscopy Database (Version 4.1) (Web, free access)   The NIST XPS Database gives access to energies of many photoelectron and Auger-electron spectral lines. The database contains over 22,000 line positions, chemical shifts, doublet splittings, and energy separations of photoelectron and Auger-electron lines.

  8. Optical and x-ray photoelectron spectroscopy studies of α-Al2O3

    NASA Astrophysics Data System (ADS)

    Prakash, Ram; Kumar, Sandeep; Kumar, Vinay; Choudhary, R. J.; Phase, D. M.

    2016-05-01

    α-Al2O3 powder sample was synthesized at 550 °C via solution combustion synthesis (SCS) method using urea as an organic fuel. The sample was characterized by X-ray diffraction (XRD), Optical spectroscopy and X-ray photoelectron spectroscopy (XPS) without any further thermal treatment. XRD study reveals that the powder crystallized directly in the hexagons α-Al2O3 phase. A band gap of 5.7 eV was estimated using diffuse reflectance spectra. For surface investigation X-ray photo electron spectroscopy (XPS) was carried out. The XPS survey scan study of α-Al2O3 powder reveals that the sample is free from impurity. The core levels of Al-2s and O-1s are also reported.

  9. Direct determination of the band offset in atomic layer deposited ZnO/hydrogenated amorphous silicon heterojunctions from X-ray photoelectron spectroscopy valence band spectra

    SciTech Connect

    Korte, L. Rößler, R.; Pettenkofer, C.

    2014-05-28

    The chemical composition and band alignment at the heterointerface between atomic layer deposition-grown zinc oxide (ZnO) and hydrogenated amorphous silicon (a-Si:H) is investigated using monochromatized X-ray photoelectron spectroscopy. A new approach for obtaining the valence band offset ΔE{sub V} is developed, which consists in fitting the valence band (VB) spectrum obtained for a-Si:H with a thin ZnO overlayer as the sum of experimentally obtained VB spectra of a bulk a-Si:H film and a thick ZnO film. This approach allows obtaining ΔE{sub V} = 2.71 ± 0.15 eV with a minimum of assumptions, and also yields information on the change in band bending of both substrate and ZnO film. The band offset results are compared to values obtained using the usual approach of comparing valence band edge-to-core level energy differences, ΔE{sub B,CL} − ΔE{sub B,VB}. Furthermore, a theoretical value for the VB offset is calculated from the concept of charge neutrality level line-up, using literature data for the charge neutrality levels and the experimentally determined ZnO/a-Si:H interface dipole. The thus obtained value of ΔE{sub V}{sup CNL} = 2.65 ± 0.3 eV agrees well with the experimental ΔE{sub V}.

  10. THEORY FOR THE XPS OF ACTINIDES

    SciTech Connect

    Bagus, Paul S.; Ilton, Eugene S.

    2013-08-01

    Two aspects of the electronic structure of actinide oxides that significantly affect the XPS spectra are described; these aspects are also important for the materials properties of the oxides. The two aspects considered are: (1) The spin-orbit coupling of the open 5f shell electrons in actinide cations and how this coupling affects the electronic structure. And, (2) the covalent character of the metal oxygen interaction in actinide compounds. Because of this covalent character, there are strong departures from the nominal oxidation states that are significantly larger in core-hole states than in the ground state. The consequences for the XPS of this covalent character are examined. A proper understanding of the way in which they influence the XPS makes it possible to use the XPS to correctly characterize the electronic structure of the oxides.

  11. XPS characterization of polymer–monocalcium aluminate interface

    SciTech Connect

    Kalina, Lukáš Másilko, Jiří; Koplík, Jan; Šoukal, František

    2014-12-15

    The aim of this paper is the introduction of a sophisticated testing method, X-ray photoelectron spectroscopy (XPS), used to study the interface between the hydrated cement phase and polymer after mechanochemical activation, which is fundamental for the creation of macro-defect-free (MDF) composites. The XPS results clearly explain the hypothesis of a chemical reaction mechanism in the interphase regions affecting the final properties of the MDF materials.

  12. Surface analysis of zeolites: An XPS, variable kinetic energy XPS, and low energy ion scattering study

    NASA Astrophysics Data System (ADS)

    Bare, Simon R.; Knop-Gericke, Axel; Teschner, Detre; Hävacker, Michael; Blume, Raoul; Rocha, Tulio; Schlögl, Robert; Chan, Ally S. Y.; Blackwell, N.; Charochak, M. E.; ter Veen, Rik; Brongersma, Hidde H.

    2016-06-01

    The surface Si/Al ratio in a series of zeolite Y samples has been obtained using laboratory XPS, synchrotron (variable kinetic energy) XPS, and low energy ion scattering (LEIS) spectroscopy. The non-destructive depth profile obtained using variable kinetic energy XPS is compared to that from the destructive argon ion bombardment depth profile from the lab XPS instrument. All of the data indicate that the near surface region of both the ammonium form and steamed Y zeolites is strongly enriched in aluminum. It is shown that when the inelastic mean free path of the photoelectrons is taken into account the laboratory XPS of aluminosilicates zeolites does not provide a true measurement of the surface stoichiometry, while variable kinetic energy XPS results in a more surface sensitive measurement. A comprehensive Si/Al concentration profile as a function of depth is developed by combining the data from the three surface characterization techniques. The LEIS spectroscopy reveals that the topmost atomic layer is further enriched in Al compared to subsequent layers.

  13. Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides

    SciTech Connect

    Bagus, Paul S.; Nelin, Constance J.; Ilton, Eugene S.

    2013-12-28

    X-ray photoelectron spectroscopy (XPS), and in particular the U4f level, has been widely used to elucidate the chemical state of uranium in various materials. In large part, previous experimental work has relied on comparing the U4f spectra of an unknown to some “standard” or using qualitative intuitive judgments on the expected behavior of the primary lines and satellite structures as a function of oxidation state and bonding environment. Such approaches are useful and can be sufficiently robust to make defensible claims. Nonetheless, there is no quantitative understanding of the chemistry and physics that control satellite structures or even the shape of the primary peaks. To address this issue, we used a rigorous, strictly ab initio theoretical approach to investigate the U(4f) XPS of U oxides with formal U(VI) and U(IV) oxidation states. Our theoretical studies are based on the electronic structures of embedded cluster models, where bonding between U and O is explicitly incorporated. We demonstrate that treatment of the many-body character of the cluster wavefunctions is essential to correctly model and interpret the U4f XPS. Here we definitively show that shake configurations, where an electron is transferred from a dominantly O2p bonding orbital into dominantly 5f or 6d antibonding orbitals, are indeed responsible for the major satellite features. Based on this rigorous theoretical framework, it is possible to establish quantitative relationships between features of the XPS spectra and the chemistry of the material.

  14. X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Gupta, A.; Kussmaul, A.

    1991-01-01

    Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

  15. Photoelectron Holography

    NASA Astrophysics Data System (ADS)

    Huismans, Ymkje

    2011-05-01

    New techniques using High Harmonic Generation (HHG) or attosecond pulses have proven to be successful in following the ultrafast motion of electrons and holes inside a molecule,. We introduce a complementary technique; photoelectron holography. This uses the phase and amplitude of the rescattered electrons to encode the structure and dynamics of the studied atom or molecule. Since photoelectron holography benefits from longer wavelengths, i.e. small photon energies, it is very suitable for systems with a small ionization potential. To demonstrate photoelectron holography, both measurements and calculations on atomic Xenon will be shown. Metastable Xenon was ionized with 7 μm light from the FELICE-free electron laser. The three dimensional momentum distribution of the photoelectrons was recorded by a Velocity Map Imaging (VMI)-spectrometer. In these momentum maps interference structures are observed that can be identified as an interference of direct and scattered electrons; a hologram of Xenon. Semi-classical calculations have demonstrated that in the hologram dynamical information of the electron and the atom is stored with a femtosecond to attosecond time resolution. Supervisor: Prof. Dr. M.J.J. Vrakking

  16. Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides

    SciTech Connect

    Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.

    2013-12-28

    A rigorous study is presented of the physical processes related to X-Ray photoelectron spectroscopy, XPS, in the 4f level of U oxides, which, as well as being of physical interest in themselves, are representative of XPS in heavy metal oxides. In particular, we present compelling evidence for a new view of the screening of core-holes that extends prior understandings. Our analysis of the screening focuses on the covalent mixing of high lying U and O orbitals as opposed to the, more common, use of orbitals that are nominally pure U or pure O. It is shown that this covalent mixing is quite different for the initial and final, core-hole, configurations and that this difference is directly related to the XPS satellite intensity. Furthermore, we show that the high-lying U d orbitals as well as the U(5f) orbital may both contribute to the core-hole screening, in contrast with previous work that has only considered screening through the U(5f) shell. The role of modifying the U-O interaction by changing the U-O distance has been investigated and an unexpected correlation between U-O distance and XPS satellite intensity has been discovered. The role of flourite and octahedral crystal structures for U(IV) oxides has been examined and relationships established between XPS features and the covalent interactions in the different structures. The physical views of XPS satellites as arising from shake processes or as arising from ligand to metal charge transfers are contrasted; our analysis provides strong support that shake processes give a more fundamental physical understanding than charge transfer. Our theoretical studies are based on rigorous, strictly ab initio determinations of the electronic structure of embedded cluster models of U oxides with formal U(VI) and U(IV) oxidation states. Our results provide a foundation that makes it possible to establish quantitative relationships between features of the XPS spectra and materials properties.

  17. Electron spectra line shape analysis of highly oriented pyrolytic graphite and nanocrystalline diamond.

    PubMed

    Lesiak, Beata; Zemek, Josef; Houdkova, Jana; Kromka, Alexander; Józwik, Adam

    2010-01-01

    The X-ray excited Auger electron spectroscopy (XAES), X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES) methods were applied in investigating samples of nanocrystalline diamond and highly oriented pyrolytic graphite of various C sp(2)/sp(3) ratios, crystallinity conditions and grain sizes. The composition at the surface was estimated from the XPS. The C sp(2)/sp(3) ratio was evaluated from the width of the XAES first derivative C KLL spectra and from fitting of XPS C 1s spectra into components. The pattern recognition (PR) method applied for analyzing the spectra line shapes exhibited high accuracy in distinguishing different carbon materials. The PR method was found to be a potentially useful approach for identification, especially important for technological applications in fields of materials engineering and for controlling the chemical reaction products during synthesis.

  18. X-ray photoelectron spectroscopy analysis of boron defects in silicon crystal: A first-principles study

    NASA Astrophysics Data System (ADS)

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2016-05-01

    We carried out a comprehensive study on the B 1s core-level X-ray photoelectron spectroscopy (XPS) binding energies and formation energies for boron defects in crystalline silicon by first-principles calculation with careful evaluation of the local potential boundary condition for the model system using the supercell corresponding to 1000 Si atoms. It is reconfirmed that the cubo-octahedral B12 cluster in silicon crystal is unstable and exists at the saddle point decaying to the icosahedral and S4 B12 clusters. The electrically active clusters without any postannealing of ion-implanted Si are identified as icosahedral B12 clusters. The experimentally proposed threefold coordinated B is also identified as a ⟨ 001 ⟩ B - Si defect. For an as-doped sample prepared by plasma doping, the calculated XPS spectra for complexes consisting of vacancies and substitutional B atoms are consistent with the experimental spectra. It is proposed that, assuming that the XPS peak at 187.1 eV is due to substitutional B (Bs), the experimental XPS peaks at 187.9 and 186.7 eV correspond to interstitial B at the H-site and ⟨ 001 ⟩ B - Si defects, respectively. In the annealed samples, the complex of Bs and interstitial Si near the T-site is proposed as a candidate for the experimental XPS peak at 188.3 eV.

  19. Interpretation of nanoparticle X-ray photoelectron intensities

    SciTech Connect

    Werner, Wolfgang S. M. Chudzicki, Maksymillian; Smekal, Werner; Powell, Cedric J.

    2014-06-16

    X-ray photoelectron (XPS) intensities have been simulated for spherical core-shell nanoparticles (NPs) in different geometrical arrangements in order to investigate the validity of commonly made assumptions for the interpretation of XPS NP intensities. The single-sphere approximation is valid for a powder sample when all spatial coordinates of the NP positions are uncorrelated. Correlations along either the depth coordinate or the lateral coordinates lead to features in the angular distribution that provide information on these correlations. The XPS intensity is proportional to the surface-to-volume ratio of nanoparticles but only for NP sizes exceeding the inelastic mean free path of the photoelectrons.

  20. In-situ NAP XPS studies of dissociative water adsorption on GaAs(100) surfaces

    NASA Astrophysics Data System (ADS)

    Ptasinska, Sylwia; Zhang, Xueqiang

    2014-03-01

    In current semiconductor-based technology it is important to design and fabricate new materials in order to achieve specific well-defined properties and functionalities. Before such systems can be applied they first need to be understood, refined and controlled. Therefore, a basic knowledge about molecule/semiconductor surface interfaces is essential. In the present work dissociative water adsorption on the GaAs(100) surface is monitored using X-ray Photoelectron Spectroscopy (XPS) performed in situ under near ambient conditions. Firstly, the crystal surface is exposed to water vapor pressures ranging from UHV to 0.5 kPa. At elevated pressures an increase of oxygenation and hydroxylation of Ga surface atoms has been observed in the Ga2p XPS spectra. Moreover, intense signals obtained from molecularly adsorbed water molecules or water molecules adsorbed via hydrogen bond to surface OH groups have been also observed in the O1s spectra. Finally, the crystal surface is annealed up to 700 K at water vapor pressure of 0.01 kPa, which leads to desorption of physisorbed water molecules and further increase of surface oxidation. The research described herein was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Basic Energy Sciences, Office of Science, United States Department of Energy through grant number DE-FC02-04ER15533.

  1. Formation of Hydroxyl and Water Layers on MgO Films Studied with Ambient Pressure XPS

    SciTech Connect

    Newberg, J.T.; Starr, D.; Yamamoto, S.; Kaya, S.; Kendelewicz, T.; Mysak, E.R.; Porsgaard, S.; Salmeron, M.B.; Brown Jr., G.E.; Nilsson, A.; Bluhm, H.

    2011-01-01

    To understand the interaction of water with MgO(100), a detailed quantitative assessment of the interfacial chemistry is necessary. We have used ambient pressure X-ray photoelectron spectroscopy (XPS) to measure molecular (H{sub 2}O) and dissociative (OH) water adsorption on a 4 monolayer (ML) thick MgO(100)/Ag(100) film under ambient conditions. Since the entire 4 ML metal oxide (Ox) film is probed by XPS, the reaction of the MgO film with water can be quantitatively studied. Using a multilayer model (Model 1) that measures changes in Ox thickness from O 1s (film) and Ag 3d (substrate) spectra, it is shown that the oxide portion of the MgO film becomes thinner upon hydroxylation. A reaction mechanism is postulated in which the top-most layer of MgO converts to Mg(OH)2 upon dissociation of water. Based on this mechanism a second model (Model 2) is developed to calculate Ox and OH thickness changes based on OH/Ox intensity ratios from O 1s spectra measured in situ, with the known initial Ox thickness prior to hydroxylation. Models 1 and 2 are applied to a 0.15 Torr isobar experiment, yielding similar results for H{sub 2}O, OH and Ox thickness changes as a function of relative humidity.

  2. Comparative study of the native oxide on 316L stainless steel by XPS and ToF-SIMS

    SciTech Connect

    Tardio, Sabrina Abel, Marie-Laure; Castle, James E.; Watts, John F.; Carr, Robert H.

    2015-09-15

    The very thin native oxide film on stainless steel, of the order of 2 nm, is known to be readily modified by immersion in aqueous media. In this paper, X-ray photoelectron spectroscopy (XPS) and time of flight secondary ions mass spectrometry are employed to investigate the nature of the air-formed film and modification after water emersion. The film is described in terms of oxide, hydroxide, and water content. The preferential dissolution of iron is shown to occur on immersion. It is shown that a water absorbed layer and a hydroxide layer are present above the oxide-like passive film. The concentrations of water and hydroxide appear to be higher in the case of exposure to water. A secure method for the peak fitting of Fe2p and Cr2p XPS spectra of such films on their metallic substrates is described. The importance of XPS survey spectra is underlined and the feasibility of C{sub 60}{sup +} SIMS depth profiling of a thin oxide layer is shown.

  3. X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms

    PubMed Central

    Pichler, Thomas; Ayala, Paola

    2015-01-01

    Summary X-ray photoelectron spectroscopy (XPS) is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS. PMID:25671162

  4. X-ray photoelectron spectroscopy of graphitic carbon nanomaterials doped with heteroatoms.

    PubMed

    Susi, Toma; Pichler, Thomas; Ayala, Paola

    2015-01-01

    X-ray photoelectron spectroscopy (XPS) is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS.

  5. Quantum mechanics/molecular mechanics modeling of photoelectron spectra: the carbon 1s core-electron binding energies of ethanol-water solutions.

    PubMed

    Löytynoja, T; Niskanen, J; Jänkälä, K; Vahtras, O; Rinkevicius, Z; Ågren, H

    2014-11-20

    Using ethanol-water solutions as illustration, we demonstrate the capability of the hybrid quantum mechanics/molecular mechanics (QM/MM) paradigm to simulate core photoelectron spectroscopy: the binding energies and the chemical shifts. An integrated approach with QM/MM binding energy calculations coupled to preceding molecular dynamics sampling is adopted to generate binding energies averaged over the solute-solvent configurations available at a particular temperature and pressure and thus allowing for a statistical assessment with confidence levels for the final binding energies. The results are analyzed in terms of the contributions in the molecular mechanics model-electrostatic, polarization, and van der Waals-with atom or bond granulation of the corresponding MM charge and polarizability force-fields. The role of extramolecular charge transfer screening of the core-hole and explicit hydrogen bonding is studied by extending the QM core to cover the first solvation shell. The results are compared to those obtained from pure electrostatic and polarizable continuum models. Particularly, the dependence of the carbon 1s binding energies with respect to the ethanol concentration is studied. Our results indicate that QM/MM can be used as an all-encompassing model to study photoelectron binding energies and chemical shifts in solvent environments.

  6. X-PEEM, XPS and ToF-SIMS characterisation of xanthate induced chalcopyrite flotation: Effect of pulp potential

    NASA Astrophysics Data System (ADS)

    Kalegowda, Yogesh; Chan, Yuet-Loy; Wei, Der-Hsin; Harmer, Sarah L.

    2015-05-01

    Synchrotron-based X-ray photoemission electron microscopy (X-PEEM), X-ray photo-electron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and ultraviolet visible spectroscopy were used to characterize the flotation behaviour of chalcopyrite with xanthate at different processing conditions. The flotation recovery of chalcopyrite decreased from 97% under oxidative conditions (Eh ~ 385 mV SHE, pH 4) to 41% at a reductive potential of - 100 mV SHE (at pH 9). X-PEEM images constructed from the metal L3 absorption edges were used to produce near-edge X-ray absorption fine structure (NEXAFS) spectra from regions of interest, allowing the variability in mineral surface chemistry of each mineral particle to be analysed, and the effect of pulp potential (Eh) on the flotation of chalcopyrite to be determined. XPS, ToF-SIMS and NEXAFS analyses of chalcopyrite particles at oxidative conditions show that the surface was mildly oxidised and covered with adsorbed molecular CuEX. The Cu 2p XPS and Cu L2,3 NEXAFS spectra were dominated by CuI species attributed to bulk chalcopyrite and adsorbed CuEX. At a reductive potential of - 100 mV SHE, an increase in concentration of CuI and FeIII oxides and hydroxides was observed. X-PEEM analysis was able to show the presence of a low percentage of CuII oxides (CuO or Cu(OH)2) with predominantly CuI oxide (Cu2O) which is not evident in Cu 2p XPS spectra.

  7. AES XPS study of chromium carbides and chromium iron carbides

    NASA Astrophysics Data System (ADS)

    Detroye, M.; Reniers, F.; Buess-Herman, C.; Vereecken, J.

    1999-04-01

    The nature of chromium rich carbides which precipitate at grain boundaries in steels is still not perfectly understood. We performed a multitechnique approach on model chromium carbide and chromium-iron carbide samples: Auger Electron Spectroscopy (AES), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and High Energy Electron Diffraction (HEED) were used to characterise the samples. Significant chemical shifts were observed for the Cr, Fe and C XPS peaks in the M 7C 3 compound (M stands for metal), indicating unambiguously that the compound formed is a mixed iron-chromium carbide.

  8. Characterization of fossil remains using XRF, XPS and XAFS spectroscopies

    NASA Astrophysics Data System (ADS)

    Zougrou, I. M.; Katsikini, M.; Pinakidou, F.; Brzhezinskaya, M.; Papadopoulou, L.; Vlachos, E.; Tsoukala, E.; Paloura, E. C.

    2016-05-01

    Synchrotron radiation micro-X-Ray Fluorescence (μ-XRF), X-ray photoelectron (XPS) and X-ray Absorption Fine Structure (XAFS) spectroscopies are applied for the study of paleontological findings. More specifically the costal plate of a gigantic terrestrial turtle Titanochelon bacharidisi and a fossilized coprolite of the cave spotted hyena Crocuta crocuta spelaea are studied. Ca L 2,3-edge NEXAFS and Ca 2p XPS are applied for the identification and quantification of apatite and Ca containing minerals. XRF mapping and XAFS are employed for the study of the spatial distribution and speciation of the minerals related to the deposition environment.

  9. Chemical state determination of molecular gallium compounds using XPS.

    PubMed

    Bourque, Jeremy L; Biesinger, Mark C; Baines, Kim M

    2016-05-01

    A series of molecular gallium compounds were analyzed using X-ray photoelectron spectroscopy (XPS). Specifically, the Ga 2p3/2 and Ga 3d5/2 photoelectron binding energies and the Ga L3M45M45 Auger electron kinetic energies of compounds with gallium in a range of assigned oxidation numbers and with different stabilizing ligands were measured. Auger parameters were calculated and used to generate multiple chemical speciation (or Wagner) plots that were subsequently used to characterize the novel gallium-cryptand[2.2.2] complexes that possess ambiguous oxidation numbers for gallium. The results presented demonstrate the ability of widely accessible XPS instruments to experimentally determine the chemical state of gallium centers and, as a consequence, provide deeper insights into reactivity compared to assigned oxidation and valence numbers.

  10. Standard Test Data and Peak Fitting for XPS Measurements

    National Institute of Standards and Technology Data Gateway

    Standard Test Data and Peak Fitting for XPS Measurements (Web, free access)   This web site provides an extensive set of simulated photoelectron spectroscopy data for users to test software for determining the positions and intensities of overlapping peaks. Users download the data, perform their analyses, and then upload their results. A Java program evaluates the results and provides a graphical presentation of the errors in the user's analyses.

  11. Particle and phase thicknesses from XPS analysis of supported bimetallic catalysts: Calcined Co-Rh/Nb{sub 2}O{sub 5}

    SciTech Connect

    Frydman, A. |; Castner, D.G.; Campbell, C.T.

    1995-03-01

    The surface structure and elemental composition of a series of calcined Co-Rh/Nb{sub 2}O{sub 5} bimetallic catalysts have been investigated using X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). New formulae for the quantitative analysis of XPS intensities for supported bimetallic catalysts involving up to three separate, layered phases on spherical support particles are used for the first time. These apply an average take-off angle for photoelectrons from spherical particles whose radii are large compared to the electron attenuation length. Calcined monometallic Co/Nb{sub 2}O{sub 5} and Rh/Nb{sub 2}O{sub 5}, and four calcined bimetallic Co-Rh/Nb{sub 2}O{sub 5} catalysts with similar Co loadings ({approx} 1.9 wt%) and variable Rh loadings (0.3 to 2.3 wt%) were examined. Reference spectra for pure CoNb{sub 2}O{sub 6} (columbite) are also presented here for the first time. The catalysts were prepared by incipient wetness impregnation and calcined at 673 K to generate the oxide precursors. The XPS lineshapes and the Co (2p) spin-orbit splitting indicated the presence of two Co species, Co{sub 3}O{sub 4} and CO{sup +2}, on all calcined Co-containing catalysts. The measured XPS Co/Nb and Rh/Nb atomic ratios for the catalysts were factors of 1.5-2 and 2-4.5, respectively, greater than the bulk atomic ratios, showing that both Co and Rh oxides were surface-enriched. The measured XPS peak intensities were compared to the values predicted from several different structural models of the oxide particles.

  12. Rondorfite-type structure — XPS and UV–vis study

    SciTech Connect

    Dulski, M.; Bilewska, K.; Wojtyniak, M.; Szade, J.; Kusz, J.; Nowak, A.; Wrzalik, R.; and others

    2015-10-15

    Highlights: • Structural and spectroscopic characterization of chlorosilicate mineral, rondorfite. • Characterization of main photoemission lines and valence band spectra. • The study of color origin’s using UV–vis spectroscopy. • Analysis of structural changes in context of origin of natural fluorescence. • Discussion of a new application possibilities of analyzed mineral - Abstract: This paper focuses on X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy of two different (green, orange) rondorfite samples. The differences in the sample color originate from various O/Cl ratios. The orange color was found to be related either to the isomorphic substitution of Fe{sup 3+}/Al{sup 3+} for Mg{sup 2+}, the presence of atypical [MgO{sub 4}] tetrahedrons in crystal structure or electronegativity of the sample. The tetrahedron is known to be very prone to accumulation of impurities and substitute atoms. Moreover, the XPS data showed tetrahedrally coordinated Mg{sup 2+} and isomorphic substitution of Al{sup 3+}/Fe{sup 3+} for Mg{sup 2+}, which influences local disordering and the point defects density and distribution. Non-equilibrium chlorine positions inside the crystal cages as well as Ca-Cl bonds have also been found. The XPS measurements as a function of temperature indicate occurrence of a structural transformation at about 770 K which is accompanied by a rotation of silicate tetrahedra within magnesiosilicate pentamer and luminescence disappearance.

  13. Effects of the low Earth orbit space environment on the surface chemistry of Kapton polyimide film: An XPS study

    NASA Technical Reports Server (NTRS)

    Lee, Myung; Rooney, William; Whiteside, James

    1992-01-01

    Kapton H (DuPont Trademark) polyimide specimens exposed to the low earth (LEO) space environment suffered significant weathering with surface erosions of approximately 8.0 microns. Despite these effects, no significant changes in bulk chemistry were observed. X-ray photoelectron spectroscopy (XPS) was used to determine local changes induced from approximately 25 percent in 1980 vintage ground control specimens to nearly 53 percent in space exposed specimens. The greatest increase was observed for the divalent oxygen moieties, although a slight increase in carbonyl oxygen was also measured. Furthermore, the chemical shifts of all XPS peaks of space-exposed Kapton are shifted to higher energy. This is consistent with a higher oxidation state of the space exposed surface. Finally, space exposed specimens had distinct silicon peaks (2p 100 eV and 2s 149 eV) in their XPS spectra in agreement with widespread reports of silicon contamination throughout the LDEF satellite. These results are discussed in terms of surface reactivity of the polyimide exposed to the LEO environment and the chemical nature of contaminants deposited on flight surfaces due to satellite outgassing.

  14. Chemical characterization of soot particles emitted by Wood-Burning Cook Stoves: A XPS and HRTEM study

    NASA Astrophysics Data System (ADS)

    Carabali, Giovanni; Peralta, Oscar; Castro, Telma; Torres, Ricardo; Ruiz, Gerardo; Molina, Luisa; Saavedra, Isabel

    2014-05-01

    The morphology, microstructure, chemical composition, and electronic structure of soot particles emitted directly from biofuel cook stoves have been studied by high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). In order to obtain freshly emitted soot particles, copper grids for Transmission Electron Microscope (TEM) were placed on the last two of an 8-stages MOUDI cascade impactor. The analysis of HRTEM micrographs revealed the nanostructure and the particle size of soot chain. Additionally, the morphology of soot particles was analyzed calculating the border-based fractal dimension (Df). Particles sampled on the first heating stage exhibit complex shapes with high values of Df, which are present as aggregates formed by carbon ceno-spheres. The XPS survey spectrum for soot particles shows that the main particle composition is carbon. We also observed differences in the carbon/oxygen (C/O) ratio of the particles, which probably depends on the combustion process efficiency of each cook-stove analyzed. The XPS C-1s spectra show carbon with two peaks that correspond to sp2 and sp3 hybridization. Also, real-time absorption (βa) and scattering (αs) coefficients of the particles emitted by cook stoves were measured. The trend in βa and αs indicate that the cooking process has two important combustion stages which varied in its flaming strength, being vigorous in the first stage and soft in the second one.

  15. Photoelectronic characterization of heterointerfaces.

    SciTech Connect

    Brumbach, Michael Todd

    2012-02-01

    In many devices such as solar cells, light emitting diodes, transistors, etc., the performance relies on the electronic structure at interfaces between materials within the device. The objective of this work was to perform robust characterization of hybrid (organic/inorganic) interfaces by tailoring the interfacial region for photoelectron spectroscopy. Self-assembled monolayers (SAM) were utilized to induce dipoles of various magnitudes at the interface. Additionally, SAMs of molecules with varying dipolar characteristics were mixed into spatially organized structures to systematically vary the apparent work function. Polymer thin films were characterized by depositing films of varying thicknesses on numerous substrates with and without interfacial modifications. Hard X-ray photoelectron spectroscopy (HAXPES) was performed to evaluate a buried interface between indium tin oxide (ITO), treated under various conditions, and poly(3-hexylthiophene) (P3HT). Conducting polymer films were found to be sufficiently conducting such that no significant charge redistribution in the polymer films was observed. Consequently, a further departure from uniform substrates was taken whereby electrically disconnected regions of the substrate presented ideally insulating interfacial contacts. In order to accomplish this novel strategy, interdigitated electrodes were used as the substrate. Conducting fingers of one half of the electrodes were electrically grounded while the other set of electrodes were electronically floating. This allowed for the evaluation of substrate charging on photoelectron spectra (SCOPES) in the presence of overlying semiconducting thin films. Such an experiment has never before been reported. This concept was developed out of the previous experiments on interfacial modification and thin film depositions and presents new opportunities for understanding chemical and electronic changes in a multitude of materials and interfaces.

  16. X-ray photoelectron spectroscopy study of cubic boron nitride single crystals grown under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Hou, Lixin; Chen, Zhanguo; Liu, Xiuhuan; Gao, Yanjun; Jia, Gang

    2012-02-01

    The defects, impurities and their bonding states of unintentionally doped cubic boron nitride (cBN) single crystals were investigated by X-ray photoelectron spectroscopy (XPS). The results indicate that nitrogen vacancy (VN) is the main native defect of the cBN crystals since the atomic ratio of B:N is always larger than 1 before Ar ion sputtering. After sputter cleaning, around 6 at% carbon, which probably comes from the growth chamber, remains in the samples as the main impurity. Carbon can substitute nitrogen lattice site and form the bonding states of Csbnd Bsbnd N or Csbnd B, which can be verified by the XPS spectra of C1s, B1s and N1s. The C impurity (acceptor) and N vacancy (donor) can compose the donor-acceptor complex to affect the electrical and optical properties of cBN crystals.

  17. Tunneling Splittings in Vibronic Structure of CH_3F^+ ( X^2E): Studied by High Resolution Photoelectron Spectra and AB Initio Theoretical Method

    NASA Astrophysics Data System (ADS)

    Mo, Yuxiang; Gao, Shuming; Dai, Zuyang; Li, Hua

    2013-06-01

    We report a combined experimental and theoretical study on the vibronic structure of CH_3F^+. The results show that the tunneling splittings of vibrational energy levels occur in CH_3F^+ due to the Jahn-Teller effect. Experimentally, we have measured a high resolution ZEKE spectrum of CH_3F up to 3500 cm^-^1 above the ground state. Theoretically, we performed an ab initio calculation based on the diabatic model. The adiabatic potential energy surfaces (APES) of CH_3F^+ have been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables. The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the APES have been used to determine the coefficients in the Taylor expansion. The spin-vibronic energy levels have been calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned based on the theoretical calculations. W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004). M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).

  18. Application of near ambient pressure gas-phase X-ray photoelectron spectroscopy to the investigation of catalytic properties of copper in methanol oxidation

    NASA Astrophysics Data System (ADS)

    Prosvirin, Igor P.; Bukhtiyarov, Andrey V.; Bluhm, Hendrik; Bukhtiyarov, Valerii I.

    2016-02-01

    Application of near ambient pressure (NAP) X-ray photoelectron spectroscopy for characterization of catalytic properties of a heterogeneous catalyst through measurement and analysis of the core-level spectra from gas phase constituents, which become measurable in submillibar pressure range, has been demonstrated for the reaction of methanol oxidation over polycrystalline copper foil. To improve the accuracy of quantitative analysis of the gas phase signals for the routine XPS spectrometer with double Al/Mg anode used in these experiments, the sample was removed from XPS analysis zone, but it was still located in high-pressure gas cell. As consequence, only gas phase peaks from reagents and reaction products have been observed in XPS spectra. Quantitative analysis of the spectra has allowed us to calculate conversions of the reagents and yields of the reaction products, or, other words, to characterize the catalytic properties of the catalyst and to track their changes with temperature. Further comparison of the catalytic properties with concentration of the surface species measured by in situ XPS in separate experiments, but under the same conditions, gives a possibility to discuss the reaction mechanisms.

  19. From photoelectron detachment spectra of BrHBr{sup −}, BrDBr{sup −} and IHI{sup −}, IDI{sup −} to vibrational bonding of BrMuBr and IMuI

    SciTech Connect

    Manz, Jörn; Sato, Kazuma; Takayanagi, Toshiyuki Yoshida, Takahiko

    2015-04-28

    Photoelectron detachment XLX{sup −}(00{sup 0}0) + hν → XLX(vib) + e{sup −} + KER (X = Br or I, L = H or D) at sufficiently low temperatures photoionizes linear dihalogen anions XLX{sup −} in the vibrational ground state (v{sub 1}v{sub 2}{sup l}v{sub 3} = 00{sup 0}0) and prepares the neutral radicals XLX(vib) in vibrational states (vib). At the same time, part of the photon energy (hν) is converted into kinetic energy release (KER) of the electron [R. B. Metz, S. E. Bradforth, and D. M. Neumark, Adv. Chem. Phys. 81, 1 (1992)]. The process may be described approximately in terms of a Franck-Condon type transfer of the vibrational wavefunction representing XLX{sup −}(00{sup 0}0) from the domain close to the minimum of its potential energy surface (PES) to the domain close to the linear transition state of the PES of the neutral XLX. As a consequence, prominent peaks of the photoelectron detachment spectra (pds) correlate with the vibrational energies E{sub XLX,vib} of states XLX(vib) which are centered at linear transition state. The corresponding vibrational quantum numbers may be labeled vib = (v{sub 1}v{sub 2}{sup l}v{sub 3}) = (00{sup 0}v{sub 3}). Accordingly, the related most prominent peaks in the pds are labeled v{sub 3}. We construct a model PES which mimics the “true” PES in the domain of transition state such that it supports vibrational states with energies E{sub XLX,pds,00{sup 0}v{sub 3}} close to the peaks of the pds labeled v{sub 3} = 0, 2, and 4. Subsequently, the same model PES is also used to calculate approximate values of the energies E{sub XMuX,00{sup 0}0} of the isotopomers XMuX(00{sup 0}0). For the heavy isotopomers XHX and XDX, it turns out that all energies E{sub XLX,00{sup 0}v{sub 3}} are above the threshold for dissociation, which means that all heavy XLX(00{sup 0}v{sub 3}) with wavefunctions centered at the transition state are unstable resonances with finite lifetimes. Turning the table, bound states of the heavy XLX are van

  20. A first-principles core-level XPS study on the boron impurities in germanium crystal

    SciTech Connect

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2013-12-04

    We systematically investigated the x-ray photoelectron spectroscopy (XPS) core-level shifts and formation energies of boron defects in germanium crystals and compared the results to those in silicon crystals. Both for XPS core-level shifts and formation energies, relationship between defects in Si and Ge is roughly linear. From the similarity in the formation energy, it is expected that the exotic clusters like icosahedral B12 exist in Ge as well as in Si.

  1. Samarium electrodeposited acetate and oxide thin films on stainless steel substrate characterized by XPS

    DOE PAGES

    Myhre, Kristian; Burns, Jonathan; Meyer, Harry; Sims, Nathan; Boll, Rose

    2016-06-01

    Characterization of a samarium thin film deposited on a stainless steel substrate using molecular electrodeposition was carried out using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. We studied two types of samarium electrodeposition samples, one as-deposited and one heated to 700 °C in an air flow. Survey scans include peaks coming from the stainless steel substrate, such as Fe and Cr. An X-ray photoelectron spectroscopy (XPS) survey spectrum, Sm 3d, C 1s, and O 1s narrow scans are shown. It was determined that the heating process decomposed the deposited Sm acetate to Sm2O3 using XPS.

  2. X-ray photoelectron spectroscopy characterization of the {omega} phase in water quenched Ti-5553 alloy

    SciTech Connect

    Qin, Dongyang; Lu, Yafeng; Zhang, Kong; Liu, Qian; Zhou, Lian

    2012-11-15

    X-ray photoelectron spectroscopy was used to investigate the {omega} phase in water quenched Ti-5553 alloy with a nominal composition of Ti-5Al-5V-5Mo-3Cr (wt.%), and the {omega} and the {beta} phase were distinguished by deconvoluting the XPS spectra of Al2p, V2p and Cr2p core level regions. In addition, it is found that the binding energy of core level electron of alloying elements shifts comparing with that of pure metals, and the fact was interpreted by charge redistribution model. X-ray photoelectron spectroscopy technique could be used to characterize the nano-scale {omega} phase in {beta} alloys. - Highlights: Black-Right-Pointing-Pointer We characterize the {omega} phase in Ti-5553 alloy by XPS. Black-Right-Pointing-Pointer Binding energy of Al2p, V2p and Cr2p electron are different in the {omega} and {beta} phase. Black-Right-Pointing-Pointer Structural difference leads to the binding energy gap.

  3. X-ray photoelectron spectroscopic investigation of nanocrystalline calcium silicate hydrates synthesised by reactive milling

    SciTech Connect

    Black, Leon . E-mail: l.black@shu.ac.uk; Garbev, Krassimir; Beuchle, Guenter; Stemmermann, Peter; Schild, Dieter

    2006-06-15

    X-ray photoelectron spectroscopy (XPS) has been used to analyse a series of mechanochemically synthesised, nanocrystalline calcium silicate hydrates (C-S-H). The samples, with Ca/Si ratios of 0.2 to 1.5, showed structural features of C-S-H(I). XPS analysis revealed changes in the extent of silicate polymerisation. Si 2p, Ca 2p and O 1s spectra showed that, unlike for the crystalline calcium silicate hydrate phases studied previously, there was no evidence of silicate sheets (Q{sup 3}) at low Ca/Si ratios. Si 2p and O 1s spectra indicated silicate depolymerisation, expressed by decreasing silicate chain length, with increasing C/S. In all spectra, peak narrowing was observed with increasing Ca/Si, indicating increased structural ordering. The rapid changes of the slope of FWHM of Si 2p, {delta} {sub Ca-Si} and {delta} {sub NBO-BO} as function of C/S ratio indicated a possible miscibility gap in the C-S-H-solid solution series between C/S 5/6 and 1. The modified Auger parameter ({alpha}') of nanocrystalline C-S-H decreased with increasing silicate polymerisation, a trend already observed studying crystalline C-S-H. Absolute values of {alpha}' were shifted about - 0.7 eV with respect to crystalline phases of equal C/S ratio, due to reduced crystallinity.

  4. Interfacial atomic site characterization by photoelectron diffraction for 4H-AlN/4H-SiC(11\\bar{2}0) heterojunction

    NASA Astrophysics Data System (ADS)

    Maejima, Naoyuki; Horita, Masahiro; Matsui, Hirosuke; Matsushita, Tomohiro; Daimon, Hiroshi; Matsui, Fumihiko

    2016-08-01

    The interfacial atomic structure of an AlN thin film on a nonpolar 4H-SiC(11\\bar{2}0) substrate grown by atomic Al and N plasma deposition was studied by photoelectron diffraction and spectroscopy. The epitaxial growth of the thin film was confirmed by the comparison of element-specific photoelectron intensity angular distributions (PIADs). Depth profiles were analyzed by angle-resolved constant-final-state-mode X-ray photoelectron spectroscopy (AR-XPS). No polar angular dependence was observed in Al 2p spectra, while an additional intermixing component was found in interface-sensitive N 1s spectra. The site-specific N 1s PIADs for the AlN film and an intermixing component were derived from two N 1s PIADs with different binding energies. We attributed the intermixing component to SiN interfacial layer sites. In order to prevent SiN growth at the interface, we deposited Al on the SiC(11\\bar{2}0) substrate prior to the AlN growth. A significant reduction in the amount of intermixing components at the AlN/SiC interface was confirmed by AR-XPS.

  5. Theoretical Studies on the Photoelectron and Absorption Spectra of MnO 4 and TcO 4

    SciTech Connect

    Su, Jing; Xu, Wen-Hua; Xu, Chao-Fei; Schwarz, W. H. E.; Li, Jun

    2013-09-03

    The tetraoxo pertechnetate anion (TcO4-) is of great interest for nuclear waste management and radiopharmceuticals. To elucidate its electronic structure and to compare with that of its lighter congener MnO4-, the photoelectron and electronic absorption spectra of MnO4 - and TcO4 - are investigated with density functional theory (DFT) and ab initio wave function theory (WFT). The vertical electron detachment energies (VDEs) of MnO4 - obtained with the CR-EOM-CCSD(T) method are in good agreement with the lowest two experimental VDEs; the differences are less than 0.1 eV, representing a significant improvement over the IP-EOMCCSD(T) result in the literature. Combining our CCSD(T) and CR-EOMCCSD( T) results, the first five VDEs of TcO4 - are estimated between 5 and 10 eV with an estimated accuracy of about ±0.2 eV. The vertical excitation energies are determined by using TD-DFT, CR-EOM-CCSD(T), and RASPT2 methods. The excitation energies and the assignments of the spectra are analyzed and partly improved. They are compared with reported SAC-CI results and available experimental data. Both dynamic and nondynamic electron correlations are important in the ground and excited states of MnO4 - and TcO4 -. Nondynamical correlations are particularly relevant in TcO4 - for reliable prediction of excitation energies. In TcO4 - one Rydberg state interlaces but does not mix with the valence excited states, and it disappears in the condensed phase.

  6. Theoretical studies on the electronic structures and photoelectron spectra of tri-rhenium oxide clusters: Re3O(n)(-) and Re3O(n) (n=1-6).

    PubMed

    Zhou, Qi; Gong, Wei-Chao; Xie, Lu; Zheng, Cun-Gong; Zhang, Wei; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-01-01

    Density functional theory (DFT) calculations are performed to study the structural and electronic properties of tri-rhenium oxide clusters Re3On(-/0) (n=1-6). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level are carried out to search for the global minima for both the anions and the neutrals. For the anions, the first two O atoms prefer the same corner position of a Re3 triangle. Whereas, Re3O3(-) possesses a C2v symmetry with one bridging and two terminal O atoms. The next three O atoms (n=4-6) are adding sequentially on the basis of Re3O3(-) motif, i.e., adding one terminal O atom for Re3O4(-), one terminal and one bridging O atoms for Re3O5(-), and one terminal and two bridging O atoms for Re3O6(-), respectively. Their corresponding neutral species are similar to the anions in geometry except Re3O4 and Re3O5. Molecular orbital analyses are employed to investigate the chemical bonding and structural evolution in these tri-rhenium oxide clusters.

  7. Quantitative determination of the oxidation state of iron in biotite using x-ray photoelectron spectroscopy: I. Calibration

    SciTech Connect

    Raeburn, S.P.; Ilton, E.S.; Veblen, D.R.

    1997-11-01

    X-ray photoelectron spectroscopy (XPS) analyses of Fe(III)/{Sigma}Fe were calibrated with nine single crystals of biotite of known Fe(III)/{Sigma}Fe content. Peak shape parameters for the component Fe{sup 2+} and Fe{sup 3+} Fe 3p peaks were obtained by a constrained lease squares fitting method that minimized the difference between Fe(III)/{Sigma}Fe determined by XPS and wet chemistry/electron microprobe (WCEM) analyses. Fe{sup 2+} and Fe{sup 3+} peak separation was estimated from the separation of minima in the second derivative of Fe 3p spectra. The single set of derived peak parameters yielded a good linear correlation (r = 0.87) between XPS and WCEM values over the sample displaying progressive oxidation during XPS analysis resulted in Fe{sup 2} and Fe{sup 3+} component peak shapes largely consistent with the constrained least squares fitting methods. Beam damage, which appeared to be restricted to three single crystals with low {Sigma}Fe, low Fe/Mg, and high Fe(II)/{Sigma}Fe, caused increases in Fe(III)/{Sigma}Fe that were proportional to the duration of sample exposure. 60 refs., 6 figs., 7 tabs.

  8. Thickness determination of molecularly thin lubricant films by angle-dependent X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Pang, Chongjun; Bai, Mingwu

    2007-03-01

    An angle-dependent X-ray photoelectron spectroscopy (XPS) method used to measure the thickness of molecularly thin lubricants was developed. The method was built based on an island model of patched overlayer on a flat substrate by using the photoemission signal solely from the lubricant film. Typical molecularly thin Zdol films on the CHx overcoat of unused commercial magnetic disks were measured to verify the metrology. The lubricant thickness determined by the metrology was equal to the recent result by thermostatic high vacuum atomic force microscopy. The measured deduction in the thickness of the molecularly thin lubricant films, successively irradiated by the monochromatic source operated at 14 kV/250 W, was as low as 1 Ǻ during the first irradiation hour. XPS spectra showed that no hydrocarbons, water or oxygen were adsorbed over the Zdol outer surfaces in the tested XPS conditions. The inelastic mean free path (IMFP) of C 1s in Zdol or in CHx was found to be independent of take off angle (TOA) when TOA < 40°. The IMFP of C 1s in Zdol was ˜63.5 Ǻ and the lubricant island thickness was ˜35 Ǻ.

  9. Ultrafast x-ray photoelectron spectroscopy in the microsecond time domain

    SciTech Connect

    Höfert, O.; Gleichweit, C.; Steinrück, H.-P.; Papp, C.

    2013-09-15

    We introduce a new approach for ultrafast in situ high-resolution X-ray photoelectron spectroscopy (XPS) to study surface processes and reaction kinetics on the microsecond timescale. The main idea is to follow the intensity at a fixed binding energy using a commercial 7 channeltron electron analyzer with a modified signal processing setup. This concept allows for flexible switching between measuring conventional XP spectra and ultrafast XPS. The experimental modifications are described in detail. As an example, we present measurements for the adsorption and desorption of CO on Pt(111), performed at the synchrotron radiation facility BESSY II, with a time resolution of 500 μs. Due to the ultrafast measurements, we are able to follow adsorption and desorption in situ at pressures of 2 × 10{sup −6} mbar and temperatures up to 500 K. The data are consistently analyzed using a simple model in line with data obtained with conventional fast XPS at temperatures below 460 K. Technically, our new approach allows measurement on even shorter timescales, down to 20 μs.

  10. Characterization of plasma fluorinated zirconia for dental applications by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Wolter, S. D.; Piascik, J. R.; Stoner, B. R.

    2011-09-01

    This paper discusses fluorination of biomedical-grade yttria-stabilized zirconia (YSZ) by sulfur hexafluoride plasma treatment and characterization of near-surface chemistry products by X-ray photoelectron spectroscopy (XPS). Deconvolution of the Zr 3d and Y 3d XPS core level spectra revealed formation of both ZrF4 and YF3. In addition, seven-coordinate ZrO2F5 and/or ZrO3F4 phases were deconvolved, retaining similar atomic coordination as the parent oxide and believed to have formed by substitutional displacement of oxygen by fluorine. No additional components attributed to yttria oxyfluoride were deconvolved. Argon ion sputter depth profiling determined the overlayer to be ∼4.0 nm in thickness, and angle resolved XPS showed no angle dependence on component percentages likely due to fluorination extending into the grain boundaries of the polycrystalline substrates. Importantly, the conversion layer did not induce any apparent change in zirconia crystallinity by inspection of Zr-O 3d5/2,3/2 peak positions and full-width-at-half-maximum values, important for retaining its desirable mechanical properties.

  11. XPS Protocol for the Characterization of Pristine and Functionalized Single Wall Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Sosa, E. D.; Allada, R.; Huffman, C. B.; Arepalli, S.

    2009-01-01

    Recent interest in developing new applications for carbon nanotubes (CNT) has fueled the need to use accurate macroscopic and nanoscopic techniques to characterize and understand their chemistry. X-ray photoelectron spectroscopy (XPS) has proved to be a useful analytical tool for nanoscale surface characterization of materials including carbon nanotubes. Recent nanotechnology research at NASA Johnson Space Center (NASA-JSC) helped to establish a characterization protocol for quality assessment for single wall carbon nanotubes (SWCNTs). Here, a review of some of the major factors of the XPS technique that can influence the quality of analytical data, suggestions for methods to maximize the quality of data obtained by XPS, and the development of a protocol for XPS characterization as a complementary technique for analyzing the purity and surface characteristics of SWCNTs is presented. The XPS protocol is then applied to a number of experiments including impurity analysis and the study of chemical modifications for SWCNTs.

  12. TEM and XPS studies on CdS/CIGS interfaces

    NASA Astrophysics Data System (ADS)

    Han, Jun-feng; Liao, Cheng; Cha, Li-mei; Jiang, Tao; Xie, Hua-mu; Zhao, Kui; Besland, M.-P.

    2014-12-01

    Copper indium gallium selenide (CIGS) was deposited by metallic precursors sputtering and subsequently submitted to a selenization process. The upper CdS layers were deposited by chemical bath deposition (CBD) technique. The CdS/CIGS interfaces were investigated by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). As checked by XPS analysis, the CIGS surface exhibited a hydroxide-terminated CdSe layer when treated with Cd Partial Electrolyte solution (Cd PE). Its thickness was roughly estimated to several nanometers. A 100 nm thick CdS layer was deposited onto CIGS surface. The TEM images revealed a clear and sharp interface between CdS and CIGS. XPS analysis showed a CIGS surface covered by a pinhole free and homogeneous CdS layer. XPS depth profile measurement of the CdS/CIGS interface did not evidence elemental inter-diffusion between the CIGS and CdS layers, in very good agreement with TEM observations.

  13. XPS analysis of nikki N111 catalyst pellets

    SciTech Connect

    Kelly, Dan

    2007-03-26

    X-ray photoelectron spectroscopy (XPS) was performed on several pellets of Nikki N111 catalyst to determine elemental composition. Of specific interest, the Nikki MSDS for this material cites a 20 wt. % contribution from the species "Others". XPS was employed to determine more precisely the chemical composition of the pellets and search for potential catalytic metal species not identified on the MSDS. Results are tabulated in Table 1 below. XPS analysis of the chemical composition of the catalyst pellets compares favorably to the N ikki MSDS, if the assumption is made that the nickel in the catalyst is oxidized to Ni2O3. Specifically, using a 100 g sample basis, the 49 grams of nickel metal specified in the MSDS would carry 20 grams of oxygen if it were oxidized to Ni2O3, potentially accounting for the 20 wt. %"Others". XPS was able to confirm the presence of copper and chromium in the pellets, each expected at less than 1 atomic percent and quantified at 1-3 atomic percent concentrations, but no metal species not identified by the MSDS were detected.

  14. XPS and IGC characterization of steam treated triticale straw

    NASA Astrophysics Data System (ADS)

    Zhao, Liyan; Boluk, Yaman

    2010-10-01

    The surface chemical composition and surface energy of native and steam treated triticale straws have been investigated by X-ray photoelectron spectroscopy (XPS) and inverse gas chromatography (IGC) to reveal the effect of steam treatment temperature and time. The XPS results show that the contents of C elements and C-C group on the exterior surface of native triticale straw are much higher than those on the interior surface, indicating that there was a high quantity of wax on the exterior surface of the native triticale straw. Upon steam treatment, both carbon levels and C-C groups reduce with increasing steam temperature and treatment time of the exterior surfaces. However, the effect of steam treatment on the interior surface is very limited. In terms of the surface acid and base properties, the steam treated samples exhibited higher acid and base properties than the native sample, indicating a more polar surface of the steam treated sample.

  15. The application of XPS to the study of MIC

    SciTech Connect

    Kearns, J.R.; Clayton, C.R.; Halada, G.P.; Gillow, J.B.; Francis, A.J.

    1992-01-01

    The biotic and abiotic factors that contribute to Microbiologically Influenced Corrosion (MIC) involve the transformation of chemical species at a metal surface. X-ray Photoelectron Spectroscopy (XPS) is utilized in conjunction with conventional microbiological and Quantitative Chemical Analytical techniques to better understand the effect of environmental conditions on microbial behavior as well as the ability of bacteria to alter local environmental conditions. Specifically, the interaction of Fe, Cr, Ni, Mo ions with Desulfovibrio sp. under anoxic conditions were studied. This is the first phase of a systematic study of microbial activity and the effects of alloy elements and thermo-mechanical treatments on the MIC resistance of stainless steels.

  16. Simultaneous Use Of Zr And Mg Anodes In XPS

    NASA Technical Reports Server (NTRS)

    Allgeyer, D. F.; Pratz, E. H.

    1996-01-01

    Improved x-ray source for x-ray photoelectron spectroscopy (XPS) contains both zirconium anode with beryllium window and magnesium anode with aluminum window. Previously unresolvable peaks of electron-energy spectrum become resolvable. Developed specifically for use in analyzing distributions of chemical constituents in surface layers of specimens of 2219 aluminum alloy and in determining the depths of surface oxide layers and relative proportions of aluminum and oxide in layers. Also used to study chemical constituents of surface layers in other material systems - for example, thin oxide films on silicon-based semiconductor devices, oxide films on alloys, and surface layers affecting adhesion of paints or bonding materials.

  17. XPS investigation of DNA binding to zirconium-phosphonate surfaces.

    PubMed

    Lane, Sarah M; Monot, Julien; Petit, Marc; Bujoli, Bruno; Talham, Daniel R

    2007-07-01

    The surface coverage of phosphorylated oligonucleotides immobilized on a zirconium-phosphonate surface was analyzed using X-ray photoelectron spectroscopy (XPS). By quantifying the intensity of the N 1s signal originating from the oligonucleotide and the Zr 3d peak from the metal-phosphonate surface, the surface coverage of the oligonucleotide could be calculated with a modified substrate-overlayer model. We found relatively low surface coverages indicating that once covalently bound via the terminal phosphate the polymer chain further physisorbs to the surface limiting the adsorption of additional molecules.

  18. Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

    PubMed

    Weatherup, Robert S; Eren, Baran; Hao, Yibo; Bluhm, Hendrik; Salmeron, Miquel B

    2016-05-01

    Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.

  19. XPS study of surface state of novel perovskite system Dy0.5Sr0.5Co0.8Fe0.2O3-δ as cathode for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kautkar, Pranay R.; Acharya, Smita A.; Tumram, Priya V.; Deshpande, U. P.

    2016-05-01

    In the present attempt,novel perovskite oxide Dy0.5Sr0.5Co0.8Fe0.2O3-δ (DSCF) as cathode material has been synthesized by an Ethylene glycol-citrate combined sol-gel combustion route. Orthorhombic symmetry structure is confirmed by X-ray diffraction (XRD) and data is well fitted using Rietveld refinement by Full-Prof software suite. Chemical natureof surface of DSCF has been analyzed by using X-ray photoelectron spectroscopy (XPS). XPS result shows that Dy ions are in +3 oxidation state and Sr in +2 states. However Co2p and Fe2p spectra indicates partial change in oxidation state from Co3+/Fe3+ to Co4+/Fe4+. These attribute to develop active sites on the surface for oxygen ions. O1s XPS spectra shows two oxygen peaks relatedto lattice oxygen in perovskite and absorbed oxygen in oxygen vacancy are detected. O1s spectra demonstrate the existence of adsorbed oxygen species on the surface of DSCF oxide which is quite beneficial for intermediate temperature of Solid Oxide Fuel Cell.

  20. Morphology and Chemical Composition of soot particles emitted by Wood-burning Cook-Stoves: a HRTEM, XPS and Elastic backscattering Studies.

    NASA Astrophysics Data System (ADS)

    Carabali-Sandoval, G. A., Sr.; Castro, T.; Peralta, O.; De la Cruz, W.; Días, J.; Amelines, O.; Rivera-Hernández, M.; Varela, A.; Muñoz-Muñoz, F.; Policroniades, R.; Murillo, G.; Moreno, E.

    2014-12-01

    The morphology, microstructure and the chemical composition on surface of soot particles were studied by using high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and elastic backscattering spectrometry. In order to obtain freshly soot particles emitted by home-made wood-burning cook stoves, copper grids for Transmission Electron Microscope (TEM) were placed on the last two of an 8-stages MOUDI cascade impactor. The analysis of HRTEM micrographs revealed the nanostructure and the particle size of soot particles. The XPS survey spectra show a large carbon peak around 285 eV and the oxygen signal at 533 eV. Some differences observed in the carbon/oxygen (C/O) ratio of the particles probably depend on the combustion process efficiency of each cook-stove analyzed. The C-1s XPS spectra show an asymmetric broad peak and other with low intensity that corresponds to sp2 and sp3hybridization, which were fitted with a convolution using Gaussian functions. Elastic backscattering technique allows a chemical elemental analysis of samples and confirms the presence of C, O and Si observed by XPS. Additionally, the morphological properties of soot aggregates were analyzed calculating the border-based fractal dimension (Df). Particles exhibit complex shapes with high values of Df. Also, real-time absorption (σabs) and scattering (σsct) coefficients of fine (with aerodynamic diameter < 2.5 µm) soot particles were measured. The trend in σabs and σsct indicate that the cooking process has two important combustion stages which varied in its flaming strength, being vigorous in the first stage and soft in the second one.

  1. X-ray photoelectron spectroscopy characterization of a nonsuperconducting Y-Ba-Cu-O superconductor-normal-metal-superconductor barrier material

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Hunt, B. D.; Foote, M. C.; Bajuk, L. J.

    1992-01-01

    A film of a novel nonsuperconducting Y-Ba-Cu-O (YBCO) barrier material was grown using conditions similar to those reported by Agostinelli et al. (1991) for forming a cubic semiconducting (c-YBCO) phase, and the material was characterized using X-ray photoelectron spectroscopy (XPS). A comparison of the XPS spectra of this material to those obtained from the orthorhombic and tetragonal phases of YBCO (o-YBCO and t-YBCO, respectively) showed that the barrier material had spectral characteristics different from those of o-YBCO and t-YBCO, particularly in the O 1s region. Features associated with the Cu-O chain and surface-reconstructed Cu-O planes were absent, consistent with expectations for the simple perovskite crystal structure of c-YBCO proposed by Agostinelli et al.

  2. XPS studies and photocurrent applications of alkali-metals-doped ZnO nanoparticles under visible illumination conditions

    NASA Astrophysics Data System (ADS)

    Saáedi, Abdolhossein; Yousefi, Ramin; Jamali-Sheini, Farid; Zak, Ali Khorsand; Cheraghizade, Mohsen; Mahmoudian, M. R.; Baghchesara, Mohammad Amin; Dezaki, Abbas Shirmardi

    2016-05-01

    The present work is a study about a relationship between X-ray photoelectron spectrometer (XPS) results and photocurrent intensity of alkali-metals-elements doped ZnO nanoparticles, which is carried out under visible illumination conditions. The nanoparticles were synthesized by a simple sol-gel method. Structure and morphology studies of the NPs were carried out by X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The effect of doping on the optical band-gap was investigated by using UV-visible spectrometer. The absorption peak of the doped ZnO NPs was red-shifted with respect to that of the undoped ZnO NPs. After that, the photocurrent application of the products was examined under a white light source at 2 V bias. The photocurrent results showed that, the current intensity of the ZnO NPs was increased by doping materials. However, K-doped ZnO NPs showed the highest photocurrent intensity. Finally, a discussion was carried out about the obtained photocurrent results by the O-1s spectra of the XPS of the samples. Our results suggest that the alkali-metals-doped ZnO NPs exhibit considerable promise for highly sensitive visible-light photodetectors.

  3. Characterization of YBa 2Cu 3O x using core- and valence-level XPS

    NASA Astrophysics Data System (ADS)

    Brundle, C. R.; Fowler, D. E.

    1993-12-01

    Hundreds of papers have been published involving the photoelectron spectroscopy of the high- Tc superconducting oxides since 1987. The early work, originally on bulk-sintered material, sputtered films, and later on "single crystals", concentrated on finding "unusual" features in valence- or core-level spectra to relate to electronic structure effects which might explain the superconducting mechanism. The majority of this work has not adequately taken into account the facts that (a) photoemission probes only the top few monolayers of material, and (b) in many cases the top few layers are completely unrepresentative of the bulk material. This is particularly true for YBa 2Cu 3O x, where the surface is extremely reactive, unstable, and prone to contaminating phases, even when prepared under UHV conditions. This has led to a flood of misinformation concerning the true characteristic spectra of this material and their interpretation. In this paper, we present core- and valence-level XPS for YBa 2Cu 3O x single-crystal, bulk-sintered, and thin-film samples, and show that, when artifacts are eliminated, the characteristic spectra are the same, to first order, and easily allow distinction of surfaces consisting of the genuine orthorhombic phase ( x > 6.4) from those with the non-superconducting tetragonal phase ( x<6.4) or contaminant or reaction-product phases. With this information, it is possible to eliminate much of the previous literature discussion and also to follow the material changes occuring, for instance, during annealing, adsorption and reaction. We then discuss some detailed interpretations, including the DOS observed at and near EF, the explanations for the ˜1.5 eV chemical shift in Ba core-level BE between orthorhombic and tetragonal forms, and the implications of the very low O(1s) BE of the orthorhombic form.

  4. Atomic photoelectron-spectroscopy studies using synchrotron radiation

    SciTech Connect

    Kobrin, P.H.

    1983-02-01

    Photoelectron spectroscopy combined with tunable synchrotron radiation has been used to study the photoionization process in several atomic systems. The time structure of the synchrotron radiation source at the Stanford Synchrotron Radiation Laboratory (SSRL) was used to record time-of-flight (TOF) photoelectron spectra of gaseous Cd, Hg, Ne, Ar, Ba, and Mn. The use of two TOF analyzers made possible the measurement of photoelectron angular distributions as well as branching ratios and partial cross sections.

  5. The Electron-Phonon Interaction as Studied by Photoelectron Spectroscopy

    SciTech Connect

    D.W. Lynch

    2004-09-30

    With recent advances in energy and angle resolution, the effects of electron-phonon interactions are manifest in many valence-band photoelectron spectra (PES) for states near the Fermi level in metals.

  6. Investigating early stages of biocorrosion with XPS: AISI 304 stainless steel exposed to Burkholderia species

    NASA Astrophysics Data System (ADS)

    Johansson, Leena-Sisko; Saastamoinen, Tuomas

    1999-04-01

    We have investigated the interactions of an exopolymer-producing bacteria, Burkholderia sp. with polished AISI 304 stainless steel substrates using X-ray photoelectron spectroscopy (XPS). Steel coupons were exposed to the pure bacteria culture in a specially designed flowcell for 6 h during which the experiment was monitored in situ with an optical microscope. XPS results verified the formation of biofilm containing extracellular polymer on all the samples exposed to bacteria. Sputter results indicated that some ions needed for metabolic processes were trapped within the biofilm. Changes in the relative Fe concentration and Fe 2p peak shape indicated that also iron had accumulated into the biofilm.

  7. XPS study of distribution of elements between surface and volume in aluminosilicate catalysts and adsorbents

    SciTech Connect

    Chukin, G.D.; Grishin, S.A.; Kulikov, A.S.; Nefedov, B.K.; Surin, S.A.

    1986-02-01

    X-ray photoelectron spectroscopy (XPS) has been used in an investigation of the distribution of aluminum and sodium on the surface and in the volume of amorphous aluminosilicates. It has been shown that in the Na form of the aluminosilicates, the sodium and aluminum ions are localized preferentially on the surface. When the Na/sup +/ ions are replaced by protons, there is a change in the electronic state of the near-surface atoms in the aluminosilicates. Information on acidic centers that has been obtained by IR spectroscopy is consistent with the XPS data.

  8. Light-induced atom desorption from glass surfaces characterized by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Kumagai, Ryo; Hatakeyama, Atsushi

    2016-07-01

    We analyzed the surfaces of vitreous silica (quartz) and borosilicate glass (Pyrex) substrates exposed to rubidium (Rb) vapor by X-ray photoelectron spectroscopy (XPS) to understand the surface conditions of alkali metal vapor cells. XPS spectra indicated that Rb atoms adopted different bonding states in quartz and Pyrex. Furthermore, Rb atoms in quartz remained in the near-surface region, while they diffused into the bulk in Pyrex. For these characterized surfaces, we measured light-induced atom desorption (LIAD) of Rb atoms. Clear differences in time evolution, photon energy dependence, and substrate temperature dependence were found; the decay of LIAD by continuous ultraviolet irradiation for quartz was faster than that for Pyrex, a monotonic increase in LIAD with increasing photon energy from 1.8 to 4.3 eV was more prominent for quartz, and LIAD from quartz was more efficient at higher temperatures in the range from 300 to 580 K, while that from Pyrex was almost independent of temperature.

  9. Photoelectron spectroscopy of nitromethane anion clusters

    NASA Astrophysics Data System (ADS)

    Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

    2016-08-01

    Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

  10. Photoelectron-photoabsorption (PePa) database

    NASA Astrophysics Data System (ADS)

    Śmiałek, Małgorzata A.; Mason, Nigel J.

    2016-03-01

    In this paper a recently launched Photoelectron-Photoabsorption Database is presented. The database was developed in order to gather all the photoelectron and photoabsorption spectra measured by various collaborators over the years as well as to ease the access to the data to the potential users. In the paper the main features of the database were described and its outline explained. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  11. Photoelectron spectrometer for attosecond spectroscopy of liquids and gases

    NASA Astrophysics Data System (ADS)

    Jordan, I.; Huppert, M.; Brown, M. A.; van Bokhoven, J. A.; Wörner, H. J.

    2015-12-01

    A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectra for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup.

  12. Photoelectron spectrometer for attosecond spectroscopy of liquids and gases.

    PubMed

    Jordan, I; Huppert, M; Brown, M A; van Bokhoven, J A; Wörner, H J

    2015-12-01

    A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectra for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup. PMID:26724045

  13. Photoelectron spectrometer for attosecond spectroscopy of liquids and gases

    SciTech Connect

    Jordan, I.; Huppert, M.; Wörner, H. J.; Brown, M. A.; Bokhoven, J. A. van

    2015-12-15

    A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectra for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup.

  14. Photoelectron spectrometer for attosecond spectroscopy of liquids and gases.

    PubMed

    Jordan, I; Huppert, M; Brown, M A; van Bokhoven, J A; Wörner, H J

    2015-12-01

    A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectra for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup.

  15. Structural environment of uranium (VI) and europium (III) species sorbed onto phosphate surfaces: XPS and optical spectroscopy studies

    SciTech Connect

    Drot, R.; Simoni, E.; Alnot, M.; Ehrhardt, J.J.

    1998-09-15

    In order to characterize the structure of the surface complexes formed by interaction between uranyl and europium (III) ions and the surface of solid matrices, optical and X-ray photoelectron spectroscopies experiments on uranyl/europium loaded phosphate solids have been performed. The use of complimentary spectroscopic techniques allows an identification of the sorption mechanism and a structural characterization of the sorption sites and the sorbed species on phosphate surfaces. The samples were prepared from aqueous uranyl or europium solutions in the pH range from 1.5 to 6.0. The surface coverage was varied from 1 to 40% of a monolayer. The differences between the emission spectra of europium ions either sorbed on the surface of phosphate samples or doped inside the solid unambiguously indicates that these sorbed ions are exclusively located on the surface and that they do not migrate inside the matrix, which shows clearly that surface complexation is involved during the sorption process. The XPS spectrum of uranyl ions sorbed on zirconium diphosphate exhibits only one component, while the spectrum corresponding to uranium on thorium matrix shows two different unresolved peaks attributed to two different chemical environments. These results, corroborated by the uranyl emission spectra and the associated decay times and those obtained by optical spectroscopy of europium sorbed on the same solids, have been interpreted in terms of two sorption sites probably formed by the oxygens of the PO{sub 4} and P{sub 2}O{sub 7} surface groups.

  16. Photoelectron spectroscopy of boron aluminum hydride cluster anions

    SciTech Connect

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Gantefoer, Gerd; Bowen, Kit H. E-mail: kiran@mcneese.edu; Li, Xiang; Kiran, Boggavarapu E-mail: kiran@mcneese.edu; Kandalam, Anil K.

    2014-04-28

    Boron aluminum hydride clusters are studied through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations. Boron aluminum hydride cluster anions, B{sub x}Al{sub y}H{sub z}{sup −}, were generated in a pulsed arc cluster ionization source and identified by time-of-flight mass spectrometry. After mass selection, their photoelectron spectra were measured by a magnetic bottle-type electron energy analyzer. The resultant photoelectron spectra as well as calculations on a selected series of stoichiometries reveal significant geometrical changes upon substitution of aluminum atoms by boron atoms.

  17. Al capping layers for nondestructive x-ray photoelectron spectroscopy analyses of transition-metal nitride thin films

    SciTech Connect

    Greczynski, Grzegorz Hultman, Lars; Petrov, Ivan; Greene, J. E.

    2015-09-15

    X-ray photoelectron spectroscopy (XPS) compositional analyses of materials that have been air exposed typically require ion etching in order to remove contaminated surface layers. However, the etching step can lead to changes in sample surface and near-surface compositions due to preferential elemental sputter ejection and forward recoil implantation; this is a particular problem for metal/gas compounds and alloys such as nitrides and oxides. Here, the authors use TiN as a model system and compare XPS analysis results from three sets of polycrystalline TiN/Si(001) films deposited by reactive magnetron sputtering in a separate vacuum chamber. The films are either (1) air-exposed for ≤10 min prior to insertion into the ultrahigh-vacuum (UHV) XPS system; (2) air-exposed and subject to ion etching, using different ion energies and beam incidence angles, in the XPS chamber prior to analysis; or (3) Al-capped in-situ in the deposition system prior to air-exposure and loading into the XPS instrument. The authors show that thin, 1.5–6.0 nm, Al capping layers provide effective barriers to oxidation and contamination of TiN surfaces, thus allowing nondestructive acquisition of high-resolution core-level spectra representative of clean samples, and, hence, correct bonding assignments. The Ti 2p and N 1s satellite features, which are sensitive to ion bombardment, exhibit high intensities comparable to those obtained from single-crystal TiN/MgO(001) films grown and analyzed in-situ in a UHV XPS system and there is no indication of Al/TiN interfacial reactions. XPS-determined N/Ti concentrations acquired from Al/TiN samples agree very well with Rutherford backscattering and elastic recoil analysis results while ion-etched air-exposed samples exhibit strong N loss due to preferential resputtering. The intensities and shapes of the Ti 2p and N 1s core level signals from Al/TiN/Si(001) samples do not change following long-term (up to 70 days) exposure to ambient conditions

  18. Particle-hole cumulant approach for inelastic losses in x-ray spectra

    NASA Astrophysics Data System (ADS)

    Kas, J. J.; Rehr, J. J.; Curtis, J. B.

    2016-07-01

    Inelastic losses in core level x-ray spectra arise from many-body excitations, leading to broadening and damping as well as satellite peaks in x-ray photoemission (XPS) and x-ray absorption (XAS) spectra. Here we present a practical approach for calculating these losses based on a cumulant representation of the particle-hole Green's function, a quasiboson approximation, and a partition of the cumulant into extrinsic, intrinsic, and interference terms. The intrinsic losses are calculated using real-time time-dependent density functional theory while the extrinsic losses are obtained from the G W approximation of the photoelectron self-energy and the interference terms are approximated. These effects are included in the spectra using a convolution with an energy dependent particle-hole spectral function. The approach elucidates the nature of the spectral functions in XPS and XAS and explains the significant cancellation between extrinsic and intrinsic losses. Edge-singularity effects in metals are also accounted for. Illustrative results are presented for the XPS and XAS of both weakly and more correlated systems.

  19. Anion photoelectron spectroscopy of radicals and clusters

    SciTech Connect

    Travis, Taylor R.

    1999-12-16

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying {sup 2}{Sigma} and {sup 2}{Pi} states of C{sub 2n}H (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C{sub 2}H and C{sub 4}H. Other radicals studied include NCN and I{sub 3}. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I{sub 3} revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  20. XPS investigation of an iron/manganese/sulfated zirconia catalyst

    NASA Astrophysics Data System (ADS)

    Milburn, Diane R.; Keogh, Robert A.; Sparks, Dennis E.; Davis, Burtron H.

    1998-04-01

    A sample of Fe-Mn-SO 42--ZrO 2 has been heated at 500°C in air for 98 h. At intervals, the sample was evacuated and transferred without atmospheric exposure to an XPS chamber. As noted with Pt-SO 42--ZrO 2, the O 1s peak resolved to a doublet; one of these peaks is interpreted to result by dehydration of the sulfate group. Following the 98 h air treatment, the sample was treated at 150°C at 1 atm in flowing hydrogen for a total of 78 h. The XPS spectra, obtained at intervals during the heating in hydrogen, showed that both Fe and Mn remained in an oxidized state.

  1. X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1994-01-01

    Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

  2. A combined QCM and XPS investigation of asphaltene adsorption on metal surfaces.

    PubMed

    Rudrake, Amit; Karan, Kunal; Horton, J Hugh

    2009-04-01

    To investigate asphaltene-metal interactions, a combined quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS) study of asphaltene adsorption on a gold surface was conducted. Adsorption experiments were conducted at 25 degrees C with solutions of asphaltenes in toluene at concentrations ranging from 50 to 1500 ppm. QCM measurements yielded information on the kinetics of adsorption and further assessment of the data allowed the estimation of equilibrium adsorption levels. XPS analysis of adsorbed and bulk asphaltene demonstrated the presence of carboxylic, thiophenic, sulfide, pyridinic and pyrrolic type functional groups. The intensity of the main carbon (C-H) peak was related to surface coverage of adsorbed asphaltene as a function of asphaltene concentration by a simple mathematical model. The mass adsorption data from the QCM experiments also allowed estimation of the surface coverage, which was compared to those from XPS analyses. Surface coverage estimates as a function of asphaltene concentration could be described by a Langmuir (type-I) isotherm. The free energy of asphaltene adsorption was estimated to be -26.8+/-0.1 and -27.3+/-0.1 kJ/mol from QCM and XPS data, respectively assuming asphaltene molar mass of 750 g/gmol. QCM and XPS data was also analyzed to estimate adsorbed layer thickness after accounting for surface coverage. The thickness of the adsorbed asphaltene estimated from both XPS and QCM data analyses ranged from 6-8 nm over the entire range of adsorption concentrations investigated.

  3. Internal structure of InP/ZnS nanocrystals unraveled by high-resolution soft X-ray photoelectron spectroscopy.

    PubMed

    Huang, Kai; Demadrille, Renaud; Silly, Mathieu G; Sirotti, Fausto; Reiss, Peter; Renault, Olivier

    2010-08-24

    High-energy resolution photoelectron spectroscopy (DeltaE < 200 meV) is used to investigate the internal structure of semiconductor quantum dots containing low Z-contrast elements. In InP/ZnS core/shell nanocrystals synthesized using a single-step procedure (core and shell precursors added at the same time), a homogeneously alloyed InPZnS core structure is evidenced by quantitative analysis of their In3d(5/2) spectra recorded at variable excitation energy. When using a two-step method (core InP nanocrystal synthesis followed by subsequent ZnS shell growth), XPS analysis reveals a graded core/shell interface. We demonstrate the existence of In-S and S(x)-In-P(1-x) bonding states in both types of InP/ZnS nanocrystals, which allows a refined view on the underlying reaction mechanisms. PMID:20666468

  4. Silicon (100)/SiO2 by XPS

    SciTech Connect

    Jensen, David S.; Kanyal, Supriya S.; Madaan, Nitesh; Vail, Michael A.; Dadson, Andrew; Engelhard, Mark H.; Linford, Matthew R.

    2013-09-25

    Silicon (100) wafers are ubiquitous in microfabrication and, accordingly, their surface characteristics are important. Herein, we report the analysis of Si (100) via X-ray photoelectron spectroscopy (XPS) using monochromatic Al K radiation. Survey scans show that the material is primarily silicon and oxygen, and the Si 2p region shows two peaks that correspond to elemental silicon and silicon dioxide. Using these peaks the thickness of the native oxide (SiO2) was estimated using the equation of Strohmeier.1 The oxygen peak is symmetric. The material shows small amounts of carbon, fluorine, and nitrogen contamination. These silicon wafers are used as the base material for subsequent growth of templated carbon nanotubes.

  5. A study of reversible gamma-induced structural transformations in vitreous Ge23.5Sb11.8S64.7 by high-resolution X-ray photoelectron spectroscopy.

    PubMed

    Kovalskiy, Andriy; Jain, Himanshu; Miller, Alfred C; Golovchak, Roman Ya; Shpotyuk, Oleh I

    2006-11-16

    The structural origin of reversible gamma-induced effects in vitreous Ge(23.5)Sb(11.8)S(64.7) has been investigated by high-resolution X-ray photoelectron spectroscopy (XPS). The changes in valence band spectrum from gamma-irradiation suggest a decrease of sulfur lone pair electron concentration accompanied by changes in bonding states of S and Ge. The appearance of additional doublets in the core-level XPS spectra of Ge, Sb, and S atoms for gamma-irradiated sample is described by the formation of over- and under-coordinated charged defect pairs (Ge(3)(-)-S(3)(+)) as a result of radiation treatment. The results verify the switching of Ge-S covalent bonds into S-S bonds as the main microstructural mechanism for gamma-induced optical effects in this glass.

  6. Probing cation antisite disorder in Gd2 Ti2 O7 pyrochlore by site-specific near-edge x-ray-absorption fine structure and x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nachimuthu, P.; Thevuthasan, S.; Engelhard, M. H.; Weber, W. J.; Shuh, D. K.; Hamdan, N. M.; Mun, B. S.; Adams, E. M.; McCready, D. E.; Shutthanandan, V.; Lindle, D. W.; Balakrishnan, G.; Paul, D. M.; Gullikson, E. M.; Perera, R. C. C.; Lian, J.; Wang, L. M.; Ewing, R. C.

    2004-09-01

    Disorder in Gd2Ti2O7 is investigated by near-edge x-ray-absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS). NEXAFS shows Ti4+ ions occupy octahedral sites with a tetragonal distortion induced by vacant oxygen sites. O1s XPS spectra obtained with a charge neutralization system from Gd2Ti2O7(100) and the Gd2Ti2O7 pyrochlore used by Chen [Phys. Rev. Lett. 88, 105901 (2002)], both yielded a single peak, unlike the previous result on the latter that found two peaks. The current results give no evidence for an anisotropic distribution of Ti and O. The extra features reported in the aforementioned communication resulted from charging effects and incomplete surface cleaning. Thus, a result confirming the direct observation of simultaneous cation-anion antisite disordering and lending credence to the split vacancy model has been clarified.

  7. X-ray photoelectron spectroscopy of γ-ray-irradiated single-stranded DNA

    NASA Astrophysics Data System (ADS)

    Lee, Eunmo; Hong, W.; Han, J. H.; Choi, D. M.; Lee, Cheol Eui; Kim, H. D.; Kim, J.

    2015-07-01

    The effects of γ-ray irradiation on herring sperm single-stranded DNA have been studied by using X-ray photoelectron spectroscopy (XPS) in the view of the bonding configurations and the structural modifications. The significant changes in the hydrogen, carbon, nitrogen, and phosphorous bonding energies, as revealed by the XPS analysis, indicate that electron transfers result in the creation of radicals and in DNA strand breaks.

  8. Compact, Integrated Photoelectron Linacs

    NASA Astrophysics Data System (ADS)

    Yu, David

    2000-12-01

    The innovative compact high energy iniector which has been developed by DULY Research Inc., will have wide scientific industrial and medical applications. The new photoelectron injector integrates the photocathode directly into a multicell linear accelerator with no drift space between the injector and the linac. By focusing the beam with solenoid or permanent magnets, and producing high current with low emittance, extremely high brightness is achieved. In addition to providing a small footprint and improved beam quality in an integrated structure, the compact system considerably simplifies external subsystems required to operate the photoelectron linac, including rf power transport, beam focusing, vacuum and cooling. The photoelectron linac employs an innovative Plane-Wave-Transformer (PWT) design, which provides strong cell-to-cell coupling, relaxes manufacturing tolerance and facilitates the attachment of external ports to the compact structure with minimal field interference. DULY Research Inc. under the support of the DOE Small Business Innovation Research (SBIR) program, has developed, constructed and installed a 20-MeV, S-band compact electron source at UCLA. DULY Research is also presently engaged in the development of an X-band photoelectron linear accelerator in another SBIR project. The higher frequency structure when completed will be approximately three times smaller, and capable of a beam brightness ten times higher than the S-band structure.

  9. Chemical states in XPS and Raman analysis during removal of Cr(VI) from contaminated water by mixed maghemite-magnetite nanoparticles.

    PubMed

    Chowdhury, Saidur Rahman; Yanful, Ernest K; Pratt, Allen R

    2012-10-15

    Mixed maghemite-magnetite has been used as adsorbent for Cr(VI) removal in this study. Results show that the adsorption capacity is enhanced with an increase in reaction temperature and decrease in free energy change. Thermodynamic study shows that Cr(VI) adsorption on the mixed maghemite and magnetite is endothermic in nature and is dependent on solution pH between 3 and 6. X-ray photoelectron spectroscopy (XPS) results demonstrate the theoretical multiplet peaks for iron and chromium adsorbed iron at the surface of the γ-Fe(2)O(3) and Fe(3)O(4) mixture. Theoretical multiplet analysis shows that during Cr adsorption, the amount of maghemite increases (from 70 to 89%). In magnetite spectra, the relative content of Fe(II) decreases from 8.2 to 3.6% indicating the reduction of magnetite in the mixture particles. In Raman spectroscopy studies, clear peaks of chromium on iron oxide were generated at 826 cm(-1), which could be attributed to chemical interactions between chromium compound and iron oxide. From the results of Raman and XPS studies, electrostatic attraction and oxidation-reduction between chromium and mixed maghemite-magnetite are postulated as mechanisms for the removal of Cr(VI) from aqueous solutions. PMID:22902142

  10. Surface state modulation through wet chemical treatment as a route to controlling the electrical properties of ZnO nanowire arrays investigated with XPS

    NASA Astrophysics Data System (ADS)

    Lord, Alex M.; Maffeis, Thierry G.; Allen, Martin W.; Morgan, David; Davies, Philip R.; Jones, Daniel R.; Evans, Jonathan E.; Smith, Nathan A.; Wilks, Steve P.

    2014-11-01

    ZnO is a wide bandgap semiconductor that has many potential applications including solar cell electrodes, transparent thin film transistors and gas/biological sensors. Since the surfaces of ZnO materials have no amorphous or oxidised layers, they are very environmentally sensitive, making control of their semiconductor properties challenging. In particular, the electronic properties of ZnO nanostructures are dominated by surface effects while surface conduction layers have been observed in thin films and bulk crystals. Therefore, the ability to use the ZnO materials in a controlled way depends on the development of simple techniques to modulate their surface electronic properties. Here, we use monochromatic x-ray photoelectron spectroscopy (XPS) to investigate the use of different wet chemical treatments (EtOH, H2O2) to control the electronic properties of ZnO nanowires by modulating the surface depletion region. The valence band and core level XPS spectra are used to explore the relationship between the surface chemistry of the nanowires and the surface band bending.

  11. The investigation of the action of fillers by XPS studies of the transfer films of PEEK and its composites containing CuS and CuF2

    NASA Astrophysics Data System (ADS)

    Bahadur, S.; Gong, Deli; Anderegg, J. W.

    1993-01-01

    The wear behavior of polyetheretherketone (PEEK) and CuS-PEEK composite rubbing at 1 m/s speed and 19.6 N load against both the steel and glass disks is examined. While CuS filler decreased considerably the wear rate of PEEK in rubbing against the steel disk, the wear rate of both the filled and untilled materials in rubbing against the glass disk was almost the same. The wear rate of CuF2-PEEK composite sliding against a steel surface was also considerably lower than that of PEEK. The transfer films of the polymer and its composites containing CuS and CuF2 formed against the steel disk surfaces were studied by X-ray photoelectron spectroscopy (XPS). The analysis of the XPS spectra revealed that both CuS and CuF2 decomposed under the rubbing conditions. The analysis at two different depths in the transfer film of CuF2-PEEK revealed that the concentrations of Cu and FeF2 were greater close to the transfer film-counterface interface. However, there was no chemical change detected when unfilled PEEK rubbed against the steel disk surface.

  12. Angle-resolved X-ray photoelectron spectroscopy study of poly(vinylidene fluoride)/poly(N-dodecylacrylamide) Langmuir-Blodgett nanofilms

    NASA Astrophysics Data System (ADS)

    Zhu, Huie; Gao, Yu; Yamamoto, Shunsuke; Miyashita, Tokuji; Mitsuishi, Masaya

    2016-03-01

    Our earlier research prepared ferroelectric poly(vinylidene fluoride) (PVDF) homopolymer monolayers at the air-water interface using amphiphilic poly(N-dodecylacrylamide) (pDDA) nanosheets with Langmuir-Blodgett (LB) technique. However, the miscibility of solvent for PVDF with the water sub-phase in the Langmuir trough makes the film composition unclear in spite of the feeding ratio of \\text{PVDF}:\\text{pDDA} (50:1). In this study, angle-resolved X-ray photoelectron spectroscopy (AR-XPS) was used to investigate the surface chemical composition and the depth profile of the PVDF/pDDA LB nanofilms. The X-ray photoelectron spectroscopy (XPS) spectra confirmed by the detection of fluorine atoms that PVDF molecules were deposited successfully onto the substrate. The constant chemical composition with increasing takeoff angle from 15 to 75° reflects a well-regular layer structure of the PVDF LB nanofilm. The mixing ratio of \\text{PVDF}:\\text{pDDA} is 33:1, which contributes 89.8 wt % PVDF and 10.2 wt % in the PVDF/pDDA LB nanofilms.

  13. Electronic and Photoelectron Spectroscopy of Toluene

    NASA Astrophysics Data System (ADS)

    Gardner, Adrian M.; Green, Alistair M.; Tame-Reyes, Victor; Wright, Timothy G.

    2012-06-01

    Electronic and photoelectron spectra of toluene are presented and discussed. The utilization of a recently reported scheme for assigning the normal vibrations of substituted benzenes allows these spectra to be compared to those of other molecules with unprecedented clarity. Changes in vibrational activity within a series of substituted benzene molecules will be discussed, specifically the increased rate of intramolecular vibrational energy redistribution observed in molecules where the substituent is a methyl group. A. M. Gardner and T. G. Wright, J. Chem. Phys., 135, 114305 (2011)

  14. Contact-free pyroelectric measurements using x-ray photoelectron spectroscopy

    SciTech Connect

    Ehre, D.; Cohen, H.

    2013-07-29

    Non-contact pyroelectricity measurements based on x-ray photoelectron spectroscopy (XPS) are presented. Applied to Lithium Tantalate crystals, we demonstrate how the XPS-derived surface potential provides a simple probe of the desired property, free of all top-contact related difficulties. In particular, the increase in Lithium Tantalate spontaneous polarization under cooling, an experimentally challenging feature, is evaluated. We further inspect the roll of surface contaminants and the control over trapped surface charge in the XPS vacuum environment. Our approach can be extended to other non-contact probes, as well as to measuring additional electrical properties, such as piezoelectricity and ferroelectricity.

  15. Adsorption of acetic acid on ice studied by ambient-pressure XPS and partial-electron-yield NEXAFS spectroscopy at 230-240 K.

    PubMed

    Křepelová, Adéla; Bartels-Rausch, Thorsten; Brown, Matthew A; Bluhm, Hendrik; Ammann, Markus

    2013-01-17

    Ice plays a key role in the environment, and the ice-air interface influences heterogeneous chemical reactions between snowpack or cirrus clouds and the surrounding air. Soluble gases have been suspected to affect the topmost, disordered layer on ice (often referred to as a quasiliquid layer, QLL). Changes are especially expected in the hydrogen-bonding structure of water in the presence of solutes at the ice surface. Here, we used ambient-pressure X-ray photoelectron spectroscopy (XPS) to detect acetic acid at the ice surface at 230-240 K under atmospheric conditions for the first time. Electron-kinetic-energy-dependent C 1s spectra indicate that acetic acid remains confined to the topmost ice surface layers. Spectral analysis provides information about the protonation state of acetate at the ice surface. Surface-sensitive Auger-electron-yield C-edge near-edge X-ray absorption fine structure (NEXAFS) spectra were recorded to probe the molecular state of the adsorbed species. The O-edge NEXAFS spectra show only minor differences between clean ice and ice with adsorbed acetic acid and thus indicate that acetic acid does not lead to an extended disordered layer on the ice surface between 230 and 240 K.

  16. Approximations for photoelectron scattering

    NASA Astrophysics Data System (ADS)

    Fritzsche, V.

    1989-04-01

    The errors of several approximations in the theoretical approach of photoelectron scattering are systematically studied, in tungsten, for electron energies ranging from 10 to 1000 eV. The large inaccuracies of the plane-wave approximation (PWA) are substantially reduced by means of effective scattering amplitudes in the modified small-scattering-centre approximation (MSSCA). The reduced angular momentum expansion (RAME) is so accurate that it allows reliable calculations of multiple-scattering contributions for all the energies considered.

  17. Global nonresonant vibrational-photoelectron coupling in molecular photoionization

    NASA Astrophysics Data System (ADS)

    Poliakoff, Erwin; Das, Aloke; Hardy, David; Bozek, John; Aguilar, Alex; Lucchese, Robert

    2009-05-01

    Using photoelectron spectroscopy and Schwinger variational scattering theory, we have investigated the coupling between vibrational motion and the exiting photoelectron over extended ranges of photoelectron kinetic energy. Photoelectron spectroscopy is performed with vibrational resolution over uncommonly large ranges of energy (ca. 200 eV). We find clear and significant changes in vibrational branching ratios as a function of photon energy, in direct contradiction to predictions of the Franck-Condon principle. While it is well known that resonances lead to coupling between electronic and vibrational degrees of freedom, nonresonant mechanisms that result in such coupling are not expected or well-documented. Photoelectron spectra are presented for several electronic states of N2^+, CO^+, and NO^+, and we find that valence isoelectronic channels behave very differently, which is also surprising. Theoretical results indicate that Cooper minima are the underlying cause of these effects, and we are currently working to understand the reasons for the sensitivity of the Cooper minima on bond length.

  18. X-ray photoelectron spectroscopy surface analysis of aluminum ion stress in barley roots. [Hordeum vulgare

    SciTech Connect

    Millard, M.M.; Foy, C.D.; Coradetti, C.A.; Reinsel, M.D. )

    1990-06-01

    X-ray photoelectron spectroscopy (XPS) has been used to analyze root surface changes when Dayton barley (Hordeum vulgare) (Al tolerant) and Kearney barley (Al sensitive) seedlings were grown in nutrient solution in the presence and absence of 37.0 micromolar Al. The electron spectra from root surfaces contained strong lines in order of decreasing intensity from organic forms of carbon, oxygen, and nitrogen and weak lines due to inorganic elements in the form of anions and cations on the surface. The surface composition of root tips from Kearney was C, 65.6%; 0, 26.8%; N, 4.4% and tips from Dayton was C, 72.7%; O, 23.6%; N, 1.9%, grown in the absence of aluminum. Electron lines characteristic of nitrate, potassium, chloride, phosphate were also present in the spectra from those roots. Dayton roots grown in the presence of 37.0 micromolar aluminum contained 2.1% aluminum while Kearney contained 1.3% aluminum. The ratio of aluminum to phosphate was close to 1.0. Dayton roots usually contained twice as much aluminum phosphate in the surface region as Kearney. Dayton may be less susceptible to Al toxic effects by accumulation of aluminum phosphate on the root surface which then acts as a barrier to the transport of aluminum into the interior of the roots.

  19. XPS determination of Mn oxidation states in Mn (hydr)oxides

    NASA Astrophysics Data System (ADS)

    Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

    2016-03-01

    Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic and redox activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a layered structure that occurs commonly in soils but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and peak-widths of each oxidation state, composed of a packet of correlated component peaks, were allowed to vary. Peak-widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated, with close agreement between Mn3s and Mn3p analyses, whereas calculations based on the Mn2p3/2 spectra gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than that for Mn2p. Consequently, fitting the Mn3p and Mn3s lines yielded robust quantification of oxidation states over a range of Mn (hydr)oxide phases. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line was found to be not appropriate for birnessites.

  20. UHV and Ambient Pressure XPS: Potentials for Mg, MgO, and Mg(OH)2 Surface Analysis

    NASA Astrophysics Data System (ADS)

    Head, Ashley R.; Schnadt, Joachim

    2016-10-01

    The surface sensitivity of x-ray photoelectron spectroscopy (XPS) has positioned the technique as a routine analysis tool for chemical and electronic structure information. Samples ranging from ideal model systems to industrial materials can be analyzed. Instrumentational developments in the past two decades have popularized ambient pressure XPS, with pressures in the tens of mbar now commonplace. Here, we briefly review the technique, including a discussion of developments that allow data collection at higher pressures. We illustrate the information XPS can provide by using examples from the literature, including MgO studies. We hope to illustrate the possibilities of ambient pressure XPS to Mg, MgO, and Mg(OH)2 systems, both in fundamental and applied studies.

  1. Oxidation and deprotonation of synthetic Fe{sup II}-Fe{sup III} (oxy)hydroxycarbonate Green Rust: An X-ray photoelectron study

    SciTech Connect

    Mullet, M. Guillemin, Y.; Ruby, C.

    2008-01-15

    X-ray photoelectron spectroscopy (XPS) was used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rusts (GRs). GRs with variable composition, i.e. Fe{sup II}{sub 6(1-x)}Fe{sup III}{sub 6x}O{sub 12}H{sub 2(7-3x)} CO{sub 3}.3H{sub 2}O where the Fe{sup III} molar fraction of the positively charged hydroxide sheets, x=[Fe(III)]/[Fe(total)] belongs to [1/3, 1], were synthesised under an inert atmosphere. The broadened Fe(2p{sub 3/2}) spectra were fitted using Gupta and Sen multiplets peaks and additional satellite and surface features. The [Fe(III)]/[Fe(total)] surface atomic ratios closely agree with the x ratios expected from the bulk composition, which gives a high degree of confidence on the validity of the proposed fitting procedure. The valence band spectra are also reported and show dependencies on iron speciation. The O(1s) spectra revealed the presence of O{sup 2-}, OH{sup -} species and adsorbed water. The hydroxyl component decreases with increasing x values, i.e. with the amount of ferric iron, while the oxide component increases. This study provides direct spectroscopic evidence of the deprotonation of hydroxyl groups that occurs simultaneously with the oxidation of ferrous iron within the GR structure. - Graphical abstract: X-ray photoelectron spectroscopy (XPS) is used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rust (GR) compounds. First spectroscopic evidence of the deprotonation of hydroxyls groups occurring simultaneously to the oxidation of Fe(II) into Fe(III) species is provided.

  2. Enhanced the photocatalytic activity of Ni-doped ZnO thin films: Morphological, optical and XPS analysis

    NASA Astrophysics Data System (ADS)

    Abdel-wahab, M. Sh.; Jilani, Asim; Yahia, I. S.; Al-Ghamdi, Attieh A.

    2016-06-01

    Pure and Ni-doped ZnO thin films with different concentration of Ni (3.5 wt%, 5 wt%, 7 wt%) were prepared by DC/RF magnetron sputtering technique. The X-rays diffraction pattern showed the polycrystalline nature of pure and Ni-doped ZnO thin films. The surface morphology of pure and Ni doped ZnO thin films were investigated through atomic force microscope, which indicated the increase in the grain dimension and surface roughness with increasing the Ni doping. The UV-Visible transmission spectra showed the decrease in the transmittance of doped ZnO thin films with the incorporation of Ni dopants. The surface and chemical state analysis of pure and Ni doped ZnO thin films were investigated by X-rays photoelectron spectroscopy (XPS). The photocatalytic activities were evaluated by an aqueous solution of methyl green dye. The tungsten lamp of 500 W was used as a source of visible light for photocatalytic study. The degradation results showed that the Ni-doped ZnO thin films exhibit highly enhanced photocatalytic activity as compared to the pure ZnO thin films. The enhanced photocatalytic activities of Ni-doped ZnO thin films were attributed to the enhanced surface area (surface defects), surface roughness and decreasing the band gap of Ni-doped ZnO thin films. Our work supports the applications of thin film metal oxides in waste water treatment.

  3. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    SciTech Connect

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound {yields} bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN{sup {minus}}, NCO{sup {minus}} and NCS{sup {minus}}. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH{sub 3}0H,F + C{sub 2}H{sub 5}OH,F + OH and F + H{sub 2}. A time dependent framework for the simulation and interpretation of the bound {yields} free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH {yields} O({sup 3}P, {sup 1}D) + HF and F + H{sub 2}. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H{sub 2} system, comparisons with three-dimensional quantum calculations are made.

  4. A comparative theoretical study on core-hole excitation spectra of azafullerene and its derivatives

    SciTech Connect

    Deng, Yunfeng; Gao, Bin; Deng, Mingsen; Luo, Yi

    2014-03-28

    The core-hole excitation spectra—near-edge x-ray absorption spectroscopy (NEXAFS), x-ray emission spectroscopy (XES), and x-ray photoelectron spectroscopy (XPS) shake-up satellites have been simulated at the level of density functional theory for the azafullerene C{sub 59}N and its derivatives (C{sub 59}N){sup +}, C{sub 59}HN, (C{sub 59}N){sub 2}, and C{sub 59}N–C{sub 60}, in which the XPS shake-up satellites were simulated using our developed equivalent core hole Kohn-Sham (ECH-KS) density functional theory approach [B. Gao, Z. Wu, and Y. Luo, J. Chem. Phys. 128, 234704 (2008)] which aims for the study of XPS shake-up satellites of large-scale molecules. Our calculated spectra are generally in good agreement with available experimental results that validates the use of the ECH-KS method in the present work. The nitrogen K-edge NEXAFS, XES, and XPS shake-up satellites spectra in general can be used as fingerprints to distinguish the azafullerene C{sub 59}N and its different derivatives. Meanwhile, different carbon K-edge spectra could also provide detailed information of (local) electronic structures of different molecules. In particular, a peak (at around 284.5 eV) in the carbon K-edge NEXAFS spectrum of the heterodimer C{sub 59}N–C{sub 60} is confirmed to be related to the electron transfer from the C{sub 59}N part to the C{sub 60} part in this charge-transfer complex.

  5. Vector potential photoelectron microscopy

    SciTech Connect

    Browning, R.

    2011-10-15

    A new class of electron microscope has been developed for the chemical microanalysis of a wide range of real world samples using photoelectron spectroscopy. Highly structured, three-dimensional samples, such as fiber mats and fracture surfaces can be imaged, as well as insulators and magnetic materials. The new microscope uses the vector potential field from a solenoid magnet as a spatial reference for imaging. A prototype instrument has demonstrated imaging of uncoated silk, magnetic steel wool, and micron-sized single strand tungsten wires.

  6. Secondary ion mass spectrometry and X-ray photoelectron spectroscopy of derivitized coal surfaces

    SciTech Connect

    Martin, R.R.; Mc Intyre, N.S.; Mac Phee, J.A.; Aye, K.T.

    1987-04-01

    Secondary Ion Mass Spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS) have been used to study the low temperature oxidation of coal. /sup 18/O has been used to trace the oxygen distribution on the coal surface. Several chemical derivations have been observed on the oxidized coal surface and the reactivity of specific regions have been monitored.

  7. High Resolution Photoelectron Spectroscopy of Au_2^- and Au_4^- by Photoelectron Imaging

    NASA Astrophysics Data System (ADS)

    Leon, Iker; Yang, Zheng; Wang, Lai-Sheng

    2013-06-01

    We report high resolution photoelectron spectra of Au_2^- and Au_4^- obtained with a newly-built photoelectron imaging apparatus. Gold anions are produced by laser vaporization and the desired specie is mass selected and focused into the collinear velocity-map imaging (VMI) lens assembly. The design of the imaging lens has allowed us to obtain less than 0.9% energy resolution for high kinetic energy electrons ( > 1eV) while maintaining wavenumber resolution for low kinetic energy electrons. Although gold dimer and tetramer have been studied in the past, we present spectroscopic results under high resolution. For Au_2^-, we report high resolution spectra with an accurate determination of the electron affinity together with a complete vibrational assignment, for both the anion and neutral ground states, while for Au_4^-, we are able to resolve a low frequency mode and obtain accurately the adiabatic detachment energy.

  8. Irradiation-induced degradation of PTB7 investigated by valence band and S 2p photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Darlatt, Erik; Muhsin, Burhan; Roesch, Roland; Lupulescu, Cosmin; Roth, Friedrich; Kolbe, Michael; Gottwald, Alexander; Hoppe, Harald; Richter, Mathias

    2016-08-01

    Monochromatic radiation with known absolute radiant power from an undulator at the electron storage ring Metrology Light Source (MLS) was used to irradiate PTB7 (a thieno[3, 4-b]thiophene-alt-benzodithiophene polymer) thin films at wavelengths (photon energies) of 185 nm (6.70 eV), 220 nm (5.64 eV), 300 nm (4.13 eV), 320 nm (3.88 eV), 356 nm (3.48 eV) and 675 nm (1.84 eV) under ultra-high vacuum conditions for the investigation of radiation-induced degradation effects. The characterization of the thin films is focused at ultraviolet photoelectron spectroscopy (UPS) of valence bands and is complemented by S 2p x-ray photoelectron spectroscopy (S 2p XPS) before and after the irradiation procedure. The radiant exposure was determined for each irradiation by means of photodiodes traceably calibrated to the international system of units SI. The valence band spectra show the strongest changes for the shortest wavelengths and no degradation effect at 356 nm and 675 nm even with the highest radiant exposure applied. In the spectral range where the Sun appears bright on the Earth’s surface, no degradation effects are observed.

  9. Synchrotron-radiation XPS analysis of ultra-thin silane films: Specifying the organic silicon

    NASA Astrophysics Data System (ADS)

    Dietrich, Paul M.; Glamsch, Stephan; Ehlert, Christopher; Lippitz, Andreas; Kulak, Nora; Unger, Wolfgang E. S.

    2016-02-01

    The analysis of chemical and elemental in-depth variations in ultra-thin organic layers with thicknesses below 5 nm is very challenging. Energy- and angle-resolved XPS (ER/AR-XPS) opens up the possibility for non-destructive chemical ultra-shallow depth profiling of the outermost surface layer of ultra-thin organic films due to its exceptional surface sensitivity. For common organic materials a reliable chemical in-depth analysis with a lower limit of the XPS information depth z95 of about 1 nm can be performed. As a proof-of-principle example with relevance for industrial applications the ER/AR-XPS analysis of different organic monolayers made of amino- or benzamidosilane molecules on silicon oxide surfaces is presented. It is demonstrated how to use the Si 2p core-level region to non-destructively depth-profile the organic (silane monolayer) - inorganic (SiO2/Si) interface and how to quantify Si species, ranging from elemental silicon over native silicon oxide to the silane itself. The main advantage of the applied ER/AR-XPS method is the improved specification of organic from inorganic silicon components in Si 2p core-level spectra with exceptional low uncertainties compared to conventional laboratory XPS.

  10. X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

    NASA Astrophysics Data System (ADS)

    Bavand, R.; Yelon, A.; Sacher, E.

    2015-11-01

    Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual

  11. Deteriorated hardened cement paste structure analyzed by XPS and {sup 29}Si NMR techniques

    SciTech Connect

    Kurumisawa, Kiyofumi; Nawa, Toyoharu; Owada, Hitoshi; Shibata, Masahito

    2013-10-15

    In this report, X-ray photoelectron spectroscopy (XPS) and {sup 29}Si-MAS-NMR was used for the evaluation of deteriorated hardened cement pastes. The deterioration by ammonium nitrate solution was accompanied by changes in the pore structure as well as by structural changes in the C–S–H in the hardened cement paste. The CaO/SiO{sub 2} ratio of the C–S–H decreased with the progress of deterioration, there was also polymerization of the silicate in the C–S–H. It was confirmed that the degree of polymerization of silicate of the C–S–H in hardened cement paste can be determined by XPS. It was also shown that the polymerization depends on the structure of the C–S–H. -- Highlights: •The polymerization of silicate of the C–S–H in the HCP can be observed by XPS. •The structure of C–S–H changed with the degree of calcium leaching. •The NMR result about silicate in C–S–H was in good agreement with the XPS result.

  12. Heparin coating durability on artificial heart valves studied by XPS and antithrombin binding capacity.

    PubMed

    Kristensen, E M E; Larsson, R; Sánchez, J; Rensmo, H; Gelius, U; Siegbahn, H

    2006-04-15

    The durability and functionality of a heparin coating on artificial heart valve leaflets were evaluated with X-ray photoelectron spectroscopy (XPS) and by the coatings' capacity to bind antithrombin. Current methods for accelerated life-time testing are based on exposing leaflets to water solutions. In this paper a method is explored, in which heart valve leaflets were exposed to a continuous high shear rate (4 L/min) of human citrated plasma. It was found that the heparin coating was stable and wear resistant enough to still be present after 3 weeks and to have about the same antithrombin uptake as coatings not exposed to circulating plasma. It was, however, partly destroyed by the test as found using XPS. We suggest that heparin chains from the upper layer of heparin have been torn off from the carrier chain, in combination with loss of heparin conjugate and plasma deposition in patches. This study showed that XPS provides additional information to biological measurements such as antithrombin uptake. XPS is therefore a valuable technique not only to characterize biomaterials but also to evaluate the effect of a performance test.

  13. X-ray photoelectron spectroscopy peak assignment for perfluoropolyether oils

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1990-01-01

    Perfluoroalkylpolyether (PFPE) oils are increasingly being used as vacuum pump oils and as lubricants for magnetic recording media and instrumentation for satellites. In this paper, the relative binding energies of three PFPE oils are determined. When sample oils are continuously irradiated during X-ray spectroscopy (XPS) measurements, the relative peak intensity of the spectra is altered significantly, indicating that gaseous products form from the oils during XPS measurements. Thus, attention should be paid to chemical changes when XPE is used to characterize fluorinated carbons such as PFPE oils.

  14. Structural evolution of Ga-Ge-Te glasses by combined EXAFS and XPS analysis

    SciTech Connect

    Golovchak, R.; Calvez, L.; Bureau, B.; Jain, H.

    2013-08-07

    The structural evolution of Ga{sub x}Ge{sub y}Te{sub 100−x−y} glasses in the vicinity of GeTe{sub 4}-GaTe{sub 3} pseudo-binary tie-line is determined with high-resolution X-ray photoelectron (XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The analysis of XPS data is complicated by similar electronegativity values for the constituent chemical elements, but then the interpretation is facilitated by information from complementary EXAFS analysis of the structure around each element independently. The results show 4/4/2 coordination for Ga/Ge/Te atoms and absence of Ga(Ge)-Ge(Ga) bonds or extended Te clusters in significant concentrations within the whole range of studied composition. The observed structural features correlate well with the measured basic physical properties of Ga-containing germanium telluride glasses.

  15. Detergency of stainless steel surface soiled with human brain homogenate: an XPS study

    NASA Astrophysics Data System (ADS)

    Richard, M.; Le Mogne, Th.; Perret-Liaudet, A.; Rauwel, G.; Criquelion, J.; De Barros, M. I.; Cêtre, J. C.; Martin, J. M.

    2005-02-01

    In the detergency field of re-usable medical devices, a special attention is focused on the non conventional transmissible agent called prions which is a proteinaceous infectious agent. Few cleaning procedures are effective against prions and few techniques are available to study cleaning effectiveness with respect to proteins in general. In our study, X-ray photoelectron spectroscopy (XPS) has been used to evaluate the effectiveness of detergent formulations to remove proteins from stainless steel surface soiled with a brain homogenate (BH) from human origin. Our results showed that XPS is a reliable surface analysis technique to study chemical species remaining on surface and substrate properties after cleaning procedures. A semi-quantitative evaluation of the detergency effectiveness could also be performed.

  16. XPS and SEM characterization of electrodeposited transition metals on zirconia

    NASA Astrophysics Data System (ADS)

    Ikonomov, J.; Stoychev, D.; Marinova, Ts

    2000-07-01

    The structure and chemical composition of electrochemically deposited cobalt, copper and cobalt+copper on zirconia have been investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and scanning Auger microscopy (SAM) methods. It has been established that as-deposited metal crystallites are mainly formed on the macroconcavities of an electrochemically roughened SS 1.4301 substrate. In the facet zones, the crystallites are much smaller and have a good dispersion. In this case, the cobalt on the surface is present as Co 2+, while copper is found as Cu +. The deposited metal crystallites show no substantial changes in structure after thermal oxidation, which leads to the formation of considerably thicker oxide layers on the metal crystallites where cobalt and copper are in the Co 3+ nd Cu 2+ states. The cobalt and copper oxides obtained on ZrO 2 are characterized by good adhesion and cause no change in the specific surface area of porous zirconia films. Modification of the structure, composition and dispersion of the oxide systems under consideration is promising, with a view to their application as thin porous inorganic catalytic films.

  17. Universal quantification of elastic scattering effects in AES and XPS

    NASA Astrophysics Data System (ADS)

    Jablonski, Aleksander

    1996-09-01

    Elastic scattering of photoelectrons in a solid can be accounted for in the common formalism of XPS by introducing two correction factors, βeff and Qx. In the case of AES, only one correction factor, QA, is required. As recently shown, relatively simple analytical expressions for the correction factors can be derived from the kinetic Boltzmann equation within the so-called "transport approximation". The corrections are expressed here in terms of the ratio of the transport mean free path (TRMFP) to the inelastic mean free path (IMFP). Since the available data for the TRMFP are rather limited, it was decided to complete an extensive database of these values. They were calculated in the present work for the same elements and energies as in the IMFP tabulation published by Tanuma et al. An attempt has been made to derive a predictive formula providing the ratios of the TRMFP to the IMFP. Consequently, a very simple and accurate algorithm for calculating the correction factors βeff, Qx and QA has been developed. This algorithm can easily be generalized to multicomponent solids. The resulting values of the correction factors were found to compare very well with published values resulting from Monte Carlo calculations.

  18. A versatile photoelectron spectrometer for pressures up to 30 mbar

    SciTech Connect

    Eriksson, Susanna K.; Edström, Kristina; Hagfeldt, Anders; Hahlin, Maria; Rensmo, Håkan; Siegbahn, Hans; Kahk, Juhan Matthias; Villar-Garcia, Ignacio J.; Payne, David J.; Webb, Matthew J.; Grennberg, Helena; Yakimova, Rositza; Edwards, Mårten O. M.; Karlsson, Patrik G.; Backlund, Klas; Åhlund, John

    2014-07-15

    High-pressure photoelectron spectroscopy is a rapidly developing technique with applications in a wide range of fields ranging from fundamental surface science and catalysis to energy materials, environmental science, and biology. At present the majority of the high-pressure photoelectron spectrometers are situated at synchrotron end stations, but recently a small number of laboratory-based setups have also emerged. In this paper we discuss the design and performance of a new laboratory based high pressure photoelectron spectrometer equipped with an Al Kα X-ray anode and a hemispherical electron energy analyzer combined with a differentially pumped electrostatic lens. The instrument is demonstrated to be capable of measuring core level spectra at pressures up to 30 mbar. Moreover, valence band spectra of a silver sample as well as a carbon-coated surface (graphene) recorded under a 2 mbar nitrogen atmosphere are presented, demonstrating the versatility of this laboratory-based spectrometer.

  19. An investigation of the corrosion of polycrystalline iron by XPS, TMS and CEMS

    NASA Astrophysics Data System (ADS)

    Idczak, K.; Idczak, R.; Konieczny, R.

    2016-06-01

    The room temperature studies of polycrystalline iron exposed to air at various temperatures were performed using: the transmission Mössbauer spectroscopy (TMS), the conversion electron Mössbauer spectroscopy (CEMS) and the X-ray photoelectron spectroscopy (XPS). The unique combination of these techniques allows to determine changes of chemical composition and content of iron oxides simultaneously on the surface region, the 300 nm pre-surface region and the bulk of the samples. The results show that the chemical composition of samples changes significantly and it is strongly dependent on temperature at which the iron sample is exposed to air as well as on investigated region.

  20. Chemistry of carbon polymer composite electrode - An X-ray photoelectron spectroscopy study

    NASA Astrophysics Data System (ADS)

    Andersen, Shuang Ma; Dhiman, Rajnish; Skou, Eivind

    2015-01-01

    Surface chemistry of the electrodes in a proton exchange membrane fuel cell is of great importance for the cell performance. Many groups have reported that electrode preparation condition has a direct influence on the resulting electrode properties. In this work, the oxidation state of electrode components and the composites (catalyst ionomer mixtures) in various electrode structures were systematically studied with X-ray photoelectron spectroscopy (XPS). Based on the spectra, when catalyst is physically mixed with Nafion ionomer, the resulting electrode surface chemistry is a combination of the two components. When the electrode is prepared with a lamination procedure, the ratio between fluorocarbon and graphitic carbon is decreased. Moreover, ether type oxide content is decreased although carbon oxide is slightly increased. This indicates structure change of the catalyst layer due to an interaction between the ionomer and the catalyst and possible polymer structural change during electrode fabrication. The surface of micro porous layer was found to be much more influenced by the lamination, especially when it is in contact with catalysts in the interphase. Higher amount of platinum oxide was observed in the electrode structures (catalyst ionomer mixture) compared to the catalyst powder. This also indicates a certain interaction between the functional groups in the polymer and platinum surface.

  1. Real-time cumulant approach for inelastic losses in x-ray spectra

    NASA Astrophysics Data System (ADS)

    Kas, J. J.; Rehr, J. J.; Curtis, J. B.

    Intrinsic inelastic losses in core level x-ray absorption (XAS), emission (XES), and x-ray photo-emission spectra (XPS), arise from excitations of the system due to the sudden creation or annihilation of a deep core hole. Additional extrinsic losses arise during the propagation of the photoelectron, and interference processes are also important. These excitations are reflected in the satellite peaks observed in XPS. Formally the distribution of these excitations are described in terms of the core-hole spectral function, which can be calculated in terms of the core-hole Green's function represented in exponential form. Here we discuss an approach for calculating the exponent, or cumulant in terms of local density fluctuations via real-space, real-time time-dependent density functional theory. The role of extrinsic and interference terms is also discussed. Our method is illustrated in calculations of XAS and XPS for number of systems, including weakly correlated as well as d- and f-electron materials. Supported by DOE BES Grant DE-FG03-97ER45623.

  2. Vibrational intensity distributions in the photoelectron spectrum of hydrogen

    NASA Technical Reports Server (NTRS)

    Gardner, J. L.; Samson, J. A. R.

    1975-01-01

    The intensity distribution over the H2(+) vibrational levels up to a quantum number of 15 was measured for H2 photoelectron spectra at a photon wavelength of 584 A. The data show reasonable agreement with recent calculations only in the quantum number of 0 through 8. The higher levels are populated significantly lower than predicted by theory.

  3. Vibrational intensity distributions in the photoelectron spectrum of hydrogen

    NASA Technical Reports Server (NTRS)

    Gardner, J. L.; Samson, J. A. R.

    1976-01-01

    The intensity distribution over the H2(+) vibrational levels up to a vibrational quantum number of 15 has been measured for H2 photoelectron spectra at a photon wavelength of 584 A. The data show reasonable agreement with recent calculations only in the range of vibrational quantum numbers from 0 through 8; the higher levels are populated significantly lower than predicted by theory.

  4. The influence of surface chemistry on GSR particles: using XPS to complement SEM/EDS analytical techniques

    NASA Astrophysics Data System (ADS)

    Schwoeble, A. J.; Strohmeier, Brian R.; Piasecki, John D.

    2010-06-01

    Gunshot residue particles (GSR) were examined using scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) to illustrate the size, shape, morphology, and elemental composition normally observed in particulate resulting from a discharged firearm. Determining the presence of lead (Pb), antimony (Sb), and barium (Ba), barring other elemental tags, fused together in a single particle with the correct morphology, is all that is required for the positive identification of GSR. X-ray photoelectron spectroscopy (XPS), however, can reveal more detailed information on surface chemistry than SEM/EDS. XPS is a highly surface-sensitive (<= ~10 nm), non-destructive, analytical technique that provides qualitative information for all elements except hydrogen and helium. Nanometer-scale sampling depth and its ability to provide unique chemical state information make XPS a potential technique for providing important knowledge on the surface chemistry of GSR that complements results obtained from SEM/EDS analysis.

  5. Thin oxide-free phosphate films of composition formed on the surface of vanadium metal and characterized by x-ray photoelectron spectroscopy

    SciTech Connect

    Asunskis, D.J.; Sherwood, P.M.A.

    2006-07-15

    This article reports the preparation of thin (less than 100 A) oxide-free phosphate films of various compositions on vanadium metal. These films are interesting because of their potential for corrosion inhibition, adhesion promotion, and biocompatibility. Valence and core-level x-ray photoelectron spectroscopy (XPS) were used to characterize the films. The valence band spectra obtained were compared with spectra generated from band structure calculations for various vanadium phosphates and from previously reported spectra of vanadium phosphates. Vanadium phosphate coatings were created by the reaction of vanadium metal and different phosphorus-oxygen containing acids: H{sub 3}PO{sub 4}, H{sub 3}PO{sub 3}, H{sub 3}PO{sub 2}, and H{sub 2}P{sub 2}O{sub 7}. This article focuses upon the valence band region which shows significant differences between the four vanadium phosphate films formed as well as clear differences between the these phosphates and vanadium oxides. The valence band spectra are effectively interpreted by band structure calculations.

  6. Effects of proton irradiation on single-stranded DNA studied by using X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, E.; Lee, Cheol Eui; Han, J. H.

    2016-08-01

    X-ray photoelectron spectroscopy (XPS) has been employed in order to study the effects of proton irradiation on herring sperm single-stranded DNA. Systematic changes of the chemical shifts in the C, N, O, and P XPS line components as functions of the irradiation dose were observed, indicative of the bonding configurations in the DNA system. While the C 1 s XPS lines showed weak blueshifts, the N 1 s, O 1 s, and P 2 p XPS lines showed blueshifts with a marked dependence on the irradiation dose in a prominent manner. Our results show that linear energy transfer by charged particles and photons may have distinct molecular-level effects as the C 1 s, N 1 s, O 1 s, and P 2 p XPS lines showed redshifts in our previous study of effects of the γ-ray irradiation on the same system.

  7. Photoelectron Spectroscopy for Chemical Analysis.

    PubMed

    Rensmo, Håkan; Siegbahn, Hans

    2015-01-01

    Photoelectron spectroscopy started its modern development in the fifties based on techniques for studies of nuclear decay. Since then, photoelectron spectroscopy has undergone a dramatic expansion of application and is now a prime research tool in basic and applied science. This progress has been largely due to the concomitant development of photon sources, sample handling and electron energy analyzers. The present article describes some of the salient features of modern photoelectron spectroscopy and its applications with particular emphasis on energy relevant issues. PMID:26507085

  8. XPS for non-destructive depth profiling and 3D imaging of surface nanostructures.

    PubMed

    Hajati, Shaaker; Tougaard, Sven

    2010-04-01

    Depth profiling of nanostructures is of high importance both technologically and fundamentally. Therefore, many different methods have been developed for determination of the depth distribution of atoms, for example ion beam (e.g. O(2)(+) , Ar(+)) sputtering, low-damage C(60) cluster ion sputtering for depth profiling of organic materials, water droplet cluster ion beam depth profiling, ion-probing techniques (Rutherford backscattering spectroscopy (RBS), secondary-ion mass spectroscopy (SIMS) and glow-discharge optical emission spectroscopy (GDOES)), X-ray microanalysis using the electron probe variation technique combined with Monte Carlo calculations, angle-resolved XPS (ARXPS), and X-ray photoelectron spectroscopy (XPS) peak-shape analysis. Each of the depth profiling techniques has its own advantages and disadvantages. However, in many cases, non-destructive techniques are preferred; these include ARXPS and XPS peak-shape analysis. The former together with parallel factor analysis is suitable for giving an overall understanding of chemistry and morphology with depth. It works very well for flat surfaces but it fails for rough or nanostructured surfaces because of the shadowing effect. In the latter method shadowing effects can be avoided because only a single spectrum is used in the analysis and this may be taken at near normal emission angle. It is a rather robust means of determining atom depth distributions on the nanoscale both for large-area XPS analysis and for imaging. We critically discuss some of the techniques mentioned above and show that both ARXPS imaging and, particularly, XPS peak-shape analysis for 3D imaging of nanostructures are very promising techniques and open a gateway for visualizing nanostructures. PMID:20091159

  9. Photoelectron wave function in photoionization: plane wave or Coulomb wave?

    PubMed

    Gozem, Samer; Gunina, Anastasia O; Ichino, Takatoshi; Osborn, David L; Stanton, John F; Krylov, Anna I

    2015-11-19

    The calculation of absolute total cross sections requires accurate wave functions of the photoelectron and of the initial and final states of the system. The essential information contained in the latter two can be condensed into a Dyson orbital. We employ correlated Dyson orbitals and test approximate treatments of the photoelectron wave function, that is, plane and Coulomb waves, by comparing computed and experimental photoionization and photodetachment spectra. We find that in anions, a plane wave treatment of the photoelectron provides a good description of photodetachment spectra. For photoionization of neutral atoms or molecules with one heavy atom, the photoelectron wave function must be treated as a Coulomb wave to account for the interaction of the photoelectron with the +1 charge of the ionized core. For larger molecules, the best agreement with experiment is often achieved by using a Coulomb wave with a partial (effective) charge smaller than unity. This likely derives from the fact that the effective charge at the centroid of the Dyson orbital, which serves as the origin of the spherical wave expansion, is smaller than the total charge of a polyatomic cation. The results suggest that accurate molecular photoionization cross sections can be computed with a modified central potential model that accounts for the nonspherical charge distribution of the core by adjusting the charge in the center of the expansion.

  10. Photoelectron wave function in photoionization: plane wave or Coulomb wave?

    PubMed

    Gozem, Samer; Gunina, Anastasia O; Ichino, Takatoshi; Osborn, David L; Stanton, John F; Krylov, Anna I

    2015-11-19

    The calculation of absolute total cross sections requires accurate wave functions of the photoelectron and of the initial and final states of the system. The essential information contained in the latter two can be condensed into a Dyson orbital. We employ correlated Dyson orbitals and test approximate treatments of the photoelectron wave function, that is, plane and Coulomb waves, by comparing computed and experimental photoionization and photodetachment spectra. We find that in anions, a plane wave treatment of the photoelectron provides a good description of photodetachment spectra. For photoionization of neutral atoms or molecules with one heavy atom, the photoelectron wave function must be treated as a Coulomb wave to account for the interaction of the photoelectron with the +1 charge of the ionized core. For larger molecules, the best agreement with experiment is often achieved by using a Coulomb wave with a partial (effective) charge smaller than unity. This likely derives from the fact that the effective charge at the centroid of the Dyson orbital, which serves as the origin of the spherical wave expansion, is smaller than the total charge of a polyatomic cation. The results suggest that accurate molecular photoionization cross sections can be computed with a modified central potential model that accounts for the nonspherical charge distribution of the core by adjusting the charge in the center of the expansion. PMID:26509428

  11. Energetic (above 60 eV) atmospheric photoelectrons

    NASA Technical Reports Server (NTRS)

    Winningham, J. D.; Decker, D. T.; Kozyra, J. U.; Nagy, A. F.; Jasperse, J. R.

    1989-01-01

    Data from low altitude plasma instrument (LAPI) on Dynamics Explorer 2 document a population of high-energy (up to 800 eV) atmospheric photoelectrons that has not been reported in the published literature. The source of these photoelectrons is postulated to be the soft X-ray portion of the whole sun spectrum. This conclusion is supported by sunrise-sunset characteristics that track those of the classical (below 60 eV) EUV-produced photoelectrons, and theoretical results from two models that incorporate the soft X-ray portion of the solar spectrum. The models include K-shell ionization effects and predict peaks in the photoelectron spectrum due to Auger electrons emitted from oxygen and nitrogen. The peak for nitrogen is observed as predicted, but the peak for oxygen is barely observable. Excellent quantitative agreement is achieved between theory and experiment by using reasonable adjustments to the few published soft X-ray spectra based on solar activity. The upflowing energetic photoelectrons provide a heretofore unknown source of electrons to the magnetosphere. They occur whenever and wherever the sun is up, that is, at all invariant latitudes. Their density is low, but they are steady and ubiquitous. If scattering and trapping occur on closed field lines, then photoelectrons could contribute as a significant particle source and thus represent a new facet of magnetosphere-ionosphere coupling.

  12. Chemical and morphological characterization of TSP and PM2.5 by SEM-EDS, XPS and XRD collected in the metropolitan area of Monterrey, Mexico

    NASA Astrophysics Data System (ADS)

    González, Lucy T.; Rodríguez, F. E. Longoria; Sánchez-Domínguez, M.; Leyva-Porras, C.; Silva-Vidaurri, L. G.; Acuna-Askar, Karim; Kharisov, B. I.; Villarreal Chiu, J. F.; Alfaro Barbosa, J. M.

    2016-10-01

    Total suspended particles (TSP) and particles smaller than 2.5 μm (PM2.5) were collected at four sites in the metropolitan area of Monterrey (MAM) in Mexico. The samples were characterized by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Scanning Electron Microscopy (SEM). In order to determine the possible sources of emissions of atmospheric particulate matter, a principal component analysis (PCA) was performed. The XRD results showed that the major crystalline compounds found in the TPS were CaCO3 and SiO2; while in the PM2.5 CaSO4 was found. The XPS analysis showed that the main elements found on the surface of the particles were C, O, Si, Ca, S, and N. The deconvolution carried out on the high-resolution spectra for C1s, S2p and N1s, showed that the aromatics, sulfates and pyrrolic-amides were the main groups contributing to the signal of these elements, respectively. The C-rich particles presented a spherical morphology, while the Ca- and Si-based particles mostly showed a prismatic shape. The PCA analysis together with the results obtained from the characterization techniques, suggested that the main contributors to the CaCO3 particles collected in the PM were most probably produced and emitted into the atmosphere by local construction industries and exploitation of rich-deposits of calcite. Meanwhile, the SiO2 found in the MAM originated from the suspension of geological material abundant in the region, and the carbon particles were mainly produced by the combustion of fossil fuels.

  13. As-Received, Ozone Cleaned and Ar+ Sputtered Surfaces of Hafnium Oxide Grown by Atomic Layer Deposition and Studied by XPS

    SciTech Connect

    Engelhard, Mark H.; Herman, Jacob A.; Wallace, Robert; Baer, Donald R.

    2012-06-27

    In this study, X-ray photoelectron spectroscopy (XPS) characterization was performed on 47 nm thick hafnium oxide (HfO{sub 2}) films grown by atomic layer deposition using TEMA-Hf/H{sub 2}O at 250 C substrate temperature. HfO{sub 2} is currently being studied as a possible replacement for Silicon Oxide (SiO{sub 2}) as a gate dielectric in electronics transistors. XPS spectra were collected on a Physical Electronics Quantum 2000 Scanning ESCA Microprobe using a monochromatic Al K{sub a} X-ray (1486.7 eV) excitation source. The sample was analyzed under the following conditions: as received, after UV irradiation for five minutes, and after sputter cleaning with 2 kV Ar{sup +} ions for 180 seconds. Survey scans showed carbon, oxygen, and hafnium as the major species in the film, while the only minor species of argon and carbide was detected after sputtering. Adventitious carbon initially composed approximately 18.6 AT% of the surface, but after UV cleaning it was reduced to 2.4 AT%. This demonstrated that that the majority of carbon was due to adventitious carbon. However, after 2 kV Ar{sup +} sputtering there was still only trace amounts of carbon at {approx}1 AT%, Some of this trace carbon is now in the form of a carbide due to the interaction with Ar{sup +} used for sputter cleaning. Furthermore, the stoiciometric ratio of oxygen and hafnium is consistent with a high quality HfO{sub 2} film.

  14. XPS and STEM studies of Allende acid insoluble residues

    NASA Technical Reports Server (NTRS)

    Housley, R. M.; Clarke, D. R.

    1980-01-01

    Data on Allende acid residues obtained both before and after etching with hot HNO3 are presented. X-ray photoelectron spectra show predominantly carbonaceous material plus Fe-deficient chromite in both cases. The HNO3 oxidizes the carbonaceous material to some extent. The small chromites in these residues have a wide range of compositions somewhat paralleling those observed in larger Allende chromites and in Murchison chromites, especially in the high Al contents; however, they are deficient in divalent cations, which makes them metastable and indicates that they must have formed at relatively low temperatures. It is suggested that they formed by precipitation of Cr(3+) and Fe(3+) from olivine at low temperature or during rapid cooling.

  15. Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

    PubMed

    Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

    2015-11-17

    The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent

  16. X-ray photoelectron and Auger electron spectroscopic study of the adsorption of molecular iodine on uranium metal and uranium dioxide

    SciTech Connect

    Dillard, J.G.; Moers, H.; Klewe-Nebenius, H.; Kirch, G.; Pfennig, G.; Ache, H.J.

    1984-08-30

    The adsorption of molecular iodine on uranium metal and on uranium dioxide has been investigated at 25/sup 0/C. Clean surfaces were prepared in an ultrahigh vacuum apparatus and were characterized by X-ray photoelectron (XPS) and X-ray and electron-induced Auger electron spectroscopies (AES). Adsorption of I/sub 2/ was studied for exposures up to 100 langmuirs (1 langmuir = 10/sup -6/ torr s) on uranium metal and to 75 langmuirs on uranium dioxide. Above about 2-langmuir I/sub 2/ exposure on uranium, spectroscopic evidence is obtained to indicate the beginning of UI/sub 3/ formation. Saturation coverage for I/sub 2/ adsorption on uranium dioxide occurs at approximately 10-15 langmuirs. Analysis of the XPS and AES results as well as studies of spectra as a function of temperature lead to the conclusions that a dissociative chemisorption/reaction process occurs on uranium metal while nondissociative adsorption occurs on uranium dioxide. Variations in the iodine Auger kinetic energy and in the Auger parameter are interpreted in light of extra-atomic relaxation processes. 42 references, 10 figures, 1 table.

  17. Impact of water vapour and carbon dioxide on surface composition of C{sub 3}A polymorphs studied by X-ray photoelectron spectroscopy

    SciTech Connect

    Dubina, E.; Plank, J.; Black, L.

    2015-07-15

    The surface specific analytical method, X-ray photoelectron spectroscopy (XPS), has been used to study the effects of water vapour and CO{sub 2} on the cubic and orthorhombic polymorphs of C{sub 3}A. Significant differences between the two polymorphs were observed in the XPS spectra. Upon exposure to water vapour, both polymorphs produced C{sub 4}AH{sub 13} on their surfaces. Additionally, the sodium-doped o-C{sub 3}A developed NaOH and traces of C{sub 3}AH{sub 6} on its surface. Subsequent carbonation yielded mono carboaluminate on both polymorphs. Large amounts of Na{sub 2}CO{sub 3} also formed on the surface of o-C{sub 3}A as a result of carbonation of NaOH. Furthermore, the extent of carbonation was much more pronounced for o-C{sub 3}A{sub o} than for c-C{sub 3}A.

  18. Proton affinities and photoelectron spectra of phenylalanine and N-methyl- and N,N-dimethylphenylalanine. Correlation of lone pair ionization energies with proton affinities and implications for N-methylation as a method to effect site specific protonation of peptides

    SciTech Connect

    Campbell, S.; Marzluff, E.M.; Rodgers, M.T.; Beauchamp, J.L. ); Rempe, M.E.; Schwinck, K.F.; Lichtenberger, D.L. )

    1994-06-15

    A Fourier transform ion cyclotron resonance (FT-ICR) technique for measuring gas-phase proton affinities is presented which utilizes collisional dissociation of proton-bound clusters by off-resonance translational excitation. A simplified RRKM analysis relates unimolecular dissociation rates to proton affinities. This technique is used to measure values for the proton affinities of phenylalanine and N-methyl- and N,N-dimethylphenylalanine of 220.3, 223.6, and 224.5 kcal/mol, respectively (relative to the proton affinity of NH[sub 3] = 204.0 kcal/mol). The proton affinity measured for phenylalanine is in excellent agreement with reported literature values. The photoelectron spectra of these three molecules are also presented and analyzed. Assignments of bands to specific ionization processes are aided by comparison with model compounds such as methyl-substituted amines and 2-phenylethylamines. These data are employed to examine the correlation of adiabatic nitrogen lone pair ionization energies with gas-phase proton affinities for phenylalanine, N-methylphenylalanine, and N,N-dimethylphenylalanine in comparison to correlations for other amino acids and selected aliphatic amines. 41 refs., 7 figs., 2 tabs.

  19. Core-level spectra and molecular deformation in adsorption: V-shaped pentacene on Al(001).

    PubMed

    Baby, Anu; Lin, He; Brivio, Gian Paolo; Floreano, Luca; Fratesi, Guido

    2015-01-01

    By first-principle simulations we study the effects of molecular deformation on the electronic and spectroscopic properties as it occurs for pentacene adsorbed on the most stable site of Al(001). The rationale for the particular V-shaped deformed structure is discussed and understood. The molecule-surface bond is made evident by mapping the charge redistribution. Upon X-ray photoelectron spectroscopy (XPS) from the molecule, the bond with the surface is destabilized by the electron density rearrangement to screen the core hole. This destabilization depends on the ionized carbon atom, inducing a narrowing of the XPS spectrum with respect to the molecules adsorbed hypothetically undistorted, in full agreement to experiments. When looking instead at the near-edge X-ray absorption fine structure (NEXAFS) spectra, individual contributions from the non-equivalent C atoms provide evidence of the molecular orbital filling, hybridization, and interchange induced by distortion. The alteration of the C-C bond lengths due to the V-shaped bending decreases by a factor of two the azimuthal dichroism of NEXAFS spectra, i.e., the energy splitting of the sigma resonances measured along the two in-plane molecular axes.

  20. Core-level spectra and molecular deformation in adsorption: V-shaped pentacene on Al(001)

    PubMed Central

    Lin, He; Brivio, Gian Paolo; Floreano, Luca; Fratesi, Guido

    2015-01-01

    Summary By first-principle simulations we study the effects of molecular deformation on the electronic and spectroscopic properties as it occurs for pentacene adsorbed on the most stable site of Al(001). The rationale for the particular V-shaped deformed structure is discussed and understood. The molecule–surface bond is made evident by mapping the charge redistribution. Upon X-ray photoelectron spectroscopy (XPS) from the molecule, the bond with the surface is destabilized by the electron density rearrangement to screen the core hole. This destabilization depends on the ionized carbon atom, inducing a narrowing of the XPS spectrum with respect to the molecules adsorbed hypothetically undistorted, in full agreement to experiments. When looking instead at the near-edge X-ray absorption fine structure (NEXAFS) spectra, individual contributions from the non-equivalent C atoms provide evidence of the molecular orbital filling, hybridization, and interchange induced by distortion. The alteration of the C–C bond lengths due to the V-shaped bending decreases by a factor of two the azimuthal dichroism of NEXAFS spectra, i.e., the energy splitting of the sigma resonances measured along the two in-plane molecular axes. PMID:26734516

  1. Enhanced the photocatalytic activity of Ni-doped ZnO thin films: Morphological, optical and XPS analysis

    NASA Astrophysics Data System (ADS)

    Abdel-wahab, M. Sh.; Jilani, Asim; Yahia, I. S.; Al-Ghamdi, Attieh A.

    2016-06-01

    Pure and Ni-doped ZnO thin films with different concentration of Ni (3.5 wt%, 5 wt%, 7 wt%) were prepared by DC/RF magnetron sputtering technique. The X-rays diffraction pattern showed the polycrystalline nature of pure and Ni-doped ZnO thin films. The surface morphology of pure and Ni doped ZnO thin films were investigated through atomic force microscope, which indicated the increase in the grain dimension and surface roughness with increasing the Ni doping. The UV-Visible transmission spectra showed the decrease in the transmittance of doped ZnO thin films with the incorporation of Ni dopants. The surface and chemical state analysis of pure and Ni doped ZnO thin films were investigated by X-rays photoelectron spectroscopy (XPS). The photocatalytic activities were evaluated by an aqueous solution of methyl green dye. The tungsten lamp of 500 W was used as a source of visible light for photocatalytic study. The degradation results showed that the Ni-doped ZnO thin films exhibit highly enhanced photocatalytic activity as compared to the pure ZnO thin films. The enhanced photocatalytic activities of Ni-doped ZnO thin films were attributed to the enhanced surface area (surface defects), surface roughness and decreasing the band gap of Ni-doped ZnO thin films. Our work supports the applications of thin film metal oxides in waste water treatment.

  2. First-principles core-level X-ray photoelectron spectroscopy calculation on arsenic defects in silicon crystal

    SciTech Connect

    Kishi, Hiroki; Miyazawa, Miki; Matsushima, Naoki; Yamauchi, Jun

    2014-02-21

    We investigate the X-ray photoelectron spectroscopy (XPS) binding energies of As 3d in Si for various defects in neutral and charged states by first-principles calculation. It is found that the complexes of a substitutional As and a vacancy in charged and neutral states explain the experimentally observed unknown peak very well.

  3. A single-source precursor approach to solution processed indium arsenide thin films† †Electronic supplementary information (ESI) available: Table listing selected bond lengths and angles for InAs precursor complex. Cross-sectional SEM of InAs thin film. XPS depth profile spectra of InAs thin film. Valence band XPS of InAs thin film and standard. CCDC 1477895. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6tc02293f Click here for additional data file. Click here for additional data file.

    PubMed Central

    Marchand, Peter; Sathasivam, Sanjayan; Williamson, Benjamin A. D.; Pugh, David; Bawaked, Salem M.; Basahel, Sulaiman N.; Obaid, Abdullah Y.; Scanlon, David O.; Parkin, Ivan P.

    2016-01-01

    This paper reports the synthesis of the novel single-source precursor, [{(MeInAstBu)3}2(Me2InAs(tBu)H)2] and the subsequent first report of aerosol-assisted chemical vapour deposition of InAs thin films. Owing to the use of the single-source precursor, highly crystalline and stoichiometric films were grown at a relatively low deposition temperature of 450 °C. Core level XPS depth profiling studies showed some partial oxidation of the film surface, however this was self-limiting and disappeared on etch profiles. Valence band XPS analysis matched well with the simulated density of state spectrum. Hall effect measurements performed on the films showed that the films were n-type with promising resistivity (3.6 × 10–3 Ω cm) and carrier mobility (410 cm2 V–1 s–1) values despite growth on amorphous glass substrates. PMID:27774150

  4. Toward new techniques to measure heterogeneous oxidation of aerosol: Electrodynamic Balance-Mass Spectrometry (EDB-MS) and Aerosol X-ray Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Jacobs, M. I.; Heine, N.; Xu, B.; Davies, J. F.; Kirk, B. B.; Kostko, O.; Alayoglu, S.; Wilson, K. R.; Ahmed, M.

    2015-12-01

    The chemical composition and physical properties of aerosol can be changed via heterogeneous oxidation with the OH radical. However, the physical state of the aerosol influences the kinetics of this reaction; liquid particles with a high diffusion coefficient are expected to be well mixed and homogenously oxidized, while oxidation of solid, diffusion-limited aerosol is expected to occur primarily on the surface, creating steep chemical gradients within the particle. We are working to develop several new techniques to study the heterogeneous oxidation of different types of aerosol. We are developing a "modular" electrodynamic balance (EDB) that will enable us to study heterogeneous oxidation at aqueous interfaces using a mass-spectrometer (and potentially other detection techniques). Using a direct analysis in real time (DART) interface, preliminary droplet train measurements have demonstrated single-droplet mass spectrometry to be possible. With long reaction times in our EDB, we will be able to study heterogeneous oxidation of a wide variety of organic species in aqueous droplets. Additionally, we are working to use aerosol photoemission and velocity map imaging (VMI) to study the surface of aerosol particles as they undergo heterogeneous oxidation. With VMI, we're able to collect electrons with a 4π collection efficiency over conventional electron energy analyzers. Preliminary results looking at the ozonolysis of squalene using ultraviolet photoelectron spectroscopy (UPS) show that heterogeneous oxidation kinetic data can be extracted from photoelectron spectra. By moving to X-ray photoemission spectroscopy (XPS), we will determine elemental and chemical composition of the aerosol surface. Thus, aerosol XPS will provide information on the steep chemical gradients that form as diffusion-limited aerosol undergo heterogeneous oxidation.

  5. XPS and AFM Study of GaAs Surface Treatment

    SciTech Connect

    Contreras-Guerrero, R.; Wallace, R. M.; Aguirre-Francisco, S.; Herrera-Gomez, A.; Lopez-Lopez, M.

    2008-11-13

    Obtaining smooth and atomically clean surfaces is an important step in the preparation of a surface for device manufacturing. In this work different processes are evaluated for cleaning a GaAs surface. A good surface cleaning treatment is that which provides a high level of uniformity and controllability of the surface. Different techniques are useful as cleaning treatments depending on the growth process to be used. The goal is to remove the oxygen and carbon contaminants and then form a thin oxide film to protect the surface, which is easy to remove later with thermal desorption mechanism like molecular beam epitaxy (MBE) with minimal impact to the surface. In this study, atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) were used to characterize the structure of the surface, the composition, as well as detect oxygen and carbon contaminant on the GaAs surface. This study consists in two parts. The first part the surface was subjected to different chemical treatments. The chemical solutions were: (a)H{sub 2}SO{sub 4}:H{sub 2}O{sub 2}:H{sub 2}O(4:1:100), (b) HCl: H{sub 2}O(1:3), (c)NH{sub 4}OH 29%. The treatments (a) and (b) reduced the oxygen on the surface. Treatment (c) reduces carbon contamination. In the second part we made MOS devices on the surfaces treated. They were characterized by CV and IV electrical measurements. They show frequency dispersion.

  6. XPS and Raman study of slope-polished Cu(In,Ga)Se2 thin films

    NASA Astrophysics Data System (ADS)

    Beak, Gun Yeol; Jeon, Chan-Wook

    2016-05-01

    The growth of quality Cu(In,Ga)Se2 photovoltaic absorber without secondary phases is very important for improving the solar cell efficiency. Although X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy can identify the secondary phases, they provide insufficient information because of their insufficient resolution and complexity in analysis. In general, normal Raman spectroscopy is better for the analysis of secondary phases. On the other hand, the Raman signal provides information for film depths of less than 300 nm, and the Raman information cannot represent the properties of the entire film. In this regard, the authors introduce a new way of identifying secondary phases in Cu(In,Ga)Se2 films using depth Raman analysis. The as-prepared film was polished using a dimple grinder, which expanded a 2 μm thick film to approximately 1 mm, which is more than sufficient to resolve the depth distribution. Raman analysis indicated that the Cu(In,Ga)Se2 film showed different secondary phases, such as CuIn3Se5, InSe and CuSe, present in different depths of the film, whereas XPS provided complex information about the phases. Overall, the present study emphasizes that the Raman depth profile is more efficient for the identification of secondary phases in Cu(In,Ga)Se2 thin films than XPS and XRD. [Figure not available: see fulltext.

  7. Adsorption of Cu(II) on the (0001) plane of mica: A REFLEXAFS and XPS study

    SciTech Connect

    Farquhar, M.L.; England, K.E.R.; Vaughan, D.J.; Charnock, J.M. |

    1996-02-10

    Using reflection extended X-ray absorption fine structure spectroscopy (REFLEXAFS) and X-ray photoelectron spectroscopy (XPS) it has been established that Cu(II) in low concentration in aqueous media can be chemisorbed onto the (0001) surface of muscovite mica. From the XPS studies it is suggested that the Cu species is in a similar bonding environment to the copper in copper hydroxide. A depth profile of the reacted mica surface was also carried out using XPS and this suggests that there had been no diffusion of the Cu into the mica surface. REFLEXAFS studies of the reacted mica surface provided information about shells of O, AlSi, and Cu surrounding a central Cu absorber. The best-fit bond distances are as follows: O{single_bond}Cu, 1.98 {angstrom}; Cu{single_bond}Cu, 2.64 {angstrom}; Al/Si{single_bond}Cu, 3.09 {angstrom}. This provides direct evidence for Cu being bound to the surface at aluminate or silicate groups and suggests that the Cu species adsorbed onto the surface are similar to the copper species found in copper hydroxide, plancheite, and shattuckite. It is proposed that Cu is chemisorbed at atomic imperfections, such as steps and kinks, on the mica surface.

  8. Multiplet splitting for the XPS of heavy elements: Dependence on oxidation state

    NASA Astrophysics Data System (ADS)

    Bagus, Paul S.; Nelin, Connie J.; Al-Salik, Yahya; Ilton, Eugene S.; Idriss, Hicham

    2016-01-01

    Multiplet splittings in X-ray Photo-electron Spectroscopy, XPS, are a means of distinguishing different open shell occupations, or different oxidation states, in a material being studied. Indeed, especially for 3d transition metal complexes, they have provided fingerprints of the metal oxidation state. The present work provides theoretical and experimental evidence that it may also be possible to use multiplets to characterize the oxidation state of heavy metal, lanthanide and actinide, cations in complexes. However, it is important to make a proper choice of the XPS region to study in order to obtain large multiplet splittings. We identify a low binding energy, BE, peak that had been observed for Ce(III) in CeOx as a high spin coupled multiplet. Furthermore, we show that a low BE feature with reasonable intensity is characteristic of other XPS regions and of other metals. This feature arises from a high spin multiplet and serves as a fingerprint to distinguish closed shell from open shell cations. Evidence is presented that it may also be possible to distinguish different open shell occupations.

  9. XPS Investigation of Surface Secondary Phase Segregation in CIGS Thin Film

    SciTech Connect

    Al-Thani, H. A.; Abdullah, M. M.; Hasoon, F. S.

    2011-01-01

    Cu(In, Ga)Se{sub 2} (CIGS) thin films were deposited on Molybdenum (Mo) coated soda lime glass (SLG/Mo) substrates, using physical vapor deposition (PVD) 3-stage process. The Mo thin films were sputtered on SLG substrates using DC planar magnetron sputtering at a working gas (Ar) pressure that varies from 0.8 mT to 12 mT with a sputtering power density of 1.2 W/cm{sub 2}. The sputtering pressure of Mo thin films was varied in order to induce variations in the sputtered films morphology and porosity; as well as to subsequently induce variations in the Na out-diffusion from SLG substrate. The surface chemistry of CIGS thin films was investigated by X-Ray Photoelectron Spectroscopy (XPS). The XPS surface surveys (top 30A) and depth profiling survey (top 100A) for the elements, their chemical states, and their relative concentration were analyzed for CIGS thin films. The XPS surface analysis and composition of CIGS thin films were correlated to the bulk composition and Na out-diffusion in the CIGS films from SLG substrates.

  10. Composition-dependent structure of polycrystalline magnetron-sputtered V–Al–C–N hard coatings studied by XRD, XPS, XANES and EXAFS

    PubMed Central

    Krause, Bärbel; Darma, Susan; Kaufholz, Marthe; Mangold, Stefan; Doyle, Stephen; Ulrich, Sven; Leiste, Harald; Stüber, Michael; Baumbach, Tilo

    2013-01-01

    V–Al–C–N hard coatings with high carbon content were deposited by reactive radio-frequency magnetron sputtering using an experimental combinatorial approach, deposition from a segmented sputter target. The composition-dependent coexisting phases within the coating were analysed using the complementary methods of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS). For the analysis of the X-ray absorption near-edge spectra, a new approach for evaluation of the pre-edge peak was developed, taking into account the self-absorption effects in thin films. Within the studied composition range, a mixed face-centred cubic (V,Al)(C,N) phase coexisting with a C–C-containing phase was observed. No indication of hexagonal (V,Al)(N,C) was found. The example of V–Al–C–N demonstrates how important a combination of complementary methods is for the detection of coexisting phases in complex multi-element coatings. PMID:24046506

  11. Ultraviolet photoelectron spectroscopy analysis of lithium and deuterium interactions with graphite

    NASA Astrophysics Data System (ADS)

    Taylor, C. N.; Heim, B.; Ortoleva, S.; Allain, J. P.; Skinner, C. H.; Kugel, H. W.; Roquemore, A. L.; Kaita, R.

    2010-11-01

    Lithium wall conditioning has been implemented in fusion devices such as TFTR, CDX-U, FTU, T-11M, TJ-II and NSTX and has yielded improved plasma performance. Offline experiments at Purdue University have investigated the mechanism by which Li interacts with D. X-ray photoelectron spectroscopy (XPS) analysis has shown that deuterium irradiation induces interactions with Li-C and Li-O bonds. Ultraviolet photoelectron spectroscopy (UPS) shows Li2O 2p orbital emission energy of 6.5 eV [1]. UPS probes the outermost valence electron orbital (probe depth ˜1nm), and yields information more sensitive to chemical bonding than XPS (probe depth ˜10nm). This work examines D interaction with lithiated graphite. Additionally, high-resolution electron energy loss spectroscopy (HR-EELS) provides complementary information regarding H bond hybridization.[4pt] [1] D. Ensling et al. Applied Surface Science 255 (2008) 2517--2523.

  12. Comparative study of GeO2/Ge and SiO2/Si structures on anomalous charging of oxide films upon water adsorption revealed by ambient-pressure X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Mori, Daichi; Oka, Hiroshi; Hosoi, Takuji; Kawai, Kentaro; Morita, Mizuho; Crumlin, Ethan J.; Liu, Zhi; Watanabe, Heiji; Arima, Kenta

    2016-09-01

    The energy difference between the oxide and bulk peaks in X-ray photoelectron spectroscopy (XPS) spectra was investigated for both GeO2/Ge and SiO2/Si structures with thickness-controlled water films. This was achieved by obtaining XPS spectra at various values of relative humidity (RH) of up to ˜15%. The increase in the energy shift is more significant for thermal GeO2 on Ge than for thermal SiO2 on Si above ˜10-4% RH, which is due to the larger amount of water molecules that infiltrate into the GeO2 film to form hydroxyls. Analyzing the origins of this energy shift, we propose that the positive charging of a partially hydroxylated GeO2 film, which is unrelated to X-ray irradiation, causes the larger energy shift for GeO2/Ge than for SiO2/Si. A possible microscopic mechanism of this intrinsic positive charging is the emission of electrons from adsorbed water species in the suboxide layer of the GeO2 film to the Ge bulk, leaving immobile cations or positively charged states in the oxide. This may be related to the reported negative shift of flat band voltages in metal-oxide-semiconductor diodes with an air-exposed GeO2 layer.

  13. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E.

    2016-05-01

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  14. Solvated Electrons in Clusters: Magic Numbers for the Photoelectron Anisotropy.

    PubMed

    West, Adam H C; Yoder, Bruce L; Luckhaus, David; Signorell, Ruth

    2015-12-17

    This paper reports on a curiosity concerning magic numbers in neutral molecular clusters, namely on magic numbers related to the photoelectron anisotropy in angle-resolved photoelectron spectra. With a combination of density functional calculations and experiment, we search for magic numbers in Na(H2O)n, Na(NH3)n, Na(CH3OH)n, and Na(CH3OCH3)n clusters. In clusters of high symmetry, the highest occupied molecular orbital can be delocalized over an extended region, forming a symmetric charge distribution of high s character, which results in a pronounced anisotropy in the photoelectron angular distribution. We find magic numbers at n = 6 and 4 for sodium-doped dimethyl ether and ammonia clusters, respectively, but not for sodium-doped water and methanol clusters, which is likely a consequence of the degree of hydrogen bonding and the number of structural isomers.

  15. Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy.

    PubMed

    Seidel, Robert; Winter, Bernd; Bradforth, Stephen E

    2016-05-27

    The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

  16. Sample-morphology effects on x-ray photoelectron peak intensities. II. Estimation of detection limits for thin-film materials

    SciTech Connect

    Powell, Cedric J.; Werner, Wolfgang S. M.; Smekal, Werner

    2014-09-01

    The authors show that the National Institute of Standards and Technology database for the simulation of electron spectra for surface analysis (SESSA) can be used to determine detection limits for thin-film materials such as a thin film on a substrate or buried at varying depths in another material for common x-ray photoelectron spectroscopy (XPS) measurement conditions. Illustrative simulations were made for a W film on or in a Ru matrix and for a Ru film on or in a W matrix. In the former case, the thickness of a W film at a given depth in the Ru matrix was varied so that the intensity of the W 4d{sub 5/2} peak was essentially the same as that for a homogeneous RuW{sub 0.001} alloy. Similarly, the thickness of a Ru film at a selected depth in the W matrix was varied so that the intensity of the Ru 3p{sub 3/2} peak matched that from a homogeneous WRu{sub 0.01} alloy. These film thicknesses correspond to the detection limits of each minor component for measurement conditions where the detection limits for a homogeneous sample varied between 0.1 at. % (for the RuW{sub 0.001} alloy) and 1 at. % (for the WRu{sub 0.01} alloy). SESSA can be similarly used to convert estimates of XPS detection limits for a minor species in a homogeneous solid to the corresponding XPS detection limits for that species as a thin film on or buried in the chosen solid.

  17. Electronic structure and photoelectron spectra of osmium and ruthenium tetraoxides

    SciTech Connect

    Topol', I.A.; Vovna, V.I.; Kazachek, M.V.

    1988-01-01

    The X/sub ..cap alpha../-SW method has been used in the nonrelativistic and quasirelativistic approximations to calculate the electronic structures of OsO/sub 4/, RuO/sub 4/, and FeO/sub 4/. When the 5d element is replaced by a 4d or 3d one, the electron-density redistribution is due mainly to the d electrons. All the d electrons in FeO/sub 4/ are localized on the iron atom, which markedly reduced the ionic and covalent bonding on the transition from RuO/sub 4/ to FeO/sub 4/, which explains the instability of FeO/sub 4/. The calculated spin-orbit splittings agree well with the structure of the PES bands, which enables one to establish the sequence of MO ionization energies unambiguously.

  18. On Interpreting the Photoelectron Spectra of MgO

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Arnold, James (Technical Monitor)

    2001-01-01

    The (sup 2)Sigma(+) and (sup 2)Pi states of MgO(-) and the (sup 1)Sigma(+), (sup 1)Pi, and (sup 3)Pi states of MgO are studied using the averaged coupled-pair functional (ACPF) approach. The computed spectroscopic constants are in good agreement with the available experimental data. The computed Franck-Condon factors and photodetachment overlaps are compared with experiment.

  19. Photoelectron photoion molecular beam spectroscopy

    SciTech Connect

    Trevor, D.J.

    1980-12-01

    The use of supersonic molecular beams in photoionization mass spectroscopy and photoelectron spectroscopy to assist in the understanding of photoexcitation in the vacuum ultraviolet is described. Rotational relaxation and condensation due to supersonic expansion were shown to offer new possibilities for molecular photoionization studies. Molecular beam photoionization mass spectroscopy has been extended above 21 eV photon energy by the use of Stanford Synchrotron Radiation Laboratory (SSRL) facilities. Design considerations are discussed that have advanced the state-of-the-art in high resolution vuv photoelectron spectroscopy. To extend gas-phase studies to 160 eV photon energy, a windowless vuv-xuv beam line design is proposed.

  20. Electronic structure of rare-earth chromium antimonides RECrSb{sub 3} (RE=La-Nd, Sm, Gd-Dy, Yb) by X-ray photoelectron spectroscopy

    SciTech Connect

    Crerar, Shane J.; Mar, Arthur; Grosvenor, Andrew P.

    2012-12-15

    The electronic structure of the ternary rare-earth chromium antimonides RECrSb{sub 3} (RE=La-Nd, Sm, Gd-Dy, Yb) has been examined by high-resolution X-ray photoelectron spectroscopy (XPS) for the first time. The RE 3d or 4d core-line spectra are substantially complicated by the presence of satellite peaks but their general resemblance to those of RE{sub 2}O{sub 3} tends to support the presence of trivalent RE atoms in RECrSb{sub 3}. However, the Yb 4d spectrum of YbCrSb{sub 3} also shows peaks that are characteristic of divalent ytterbium. The Cr 2p core-line spectra exhibit asymmetric lineshapes and little change in binding energy (BE) relative to Cr metal, providing strong evidence for electronic delocalization. The Sb 3d core-line spectra reveal slightly negative BE shifts relative to elemental antimony, supporting the presence of anionic Sb species in RECrSb{sub 3}. The experimental valence band spectrum of LaCrSb{sub 3} matches well with the calculated density of states, and it can be fitted to component peaks belonging to individual atoms to yield an average formulation that agrees well with expectations ('La{sup 3+}Cr{sup 3+}(Sb{sup 2-}){sub 3}'). On progressing from LaCrSb{sub 3} to NdCrSb{sub 3}, the 4f-band in the valence band spectra grows in intensity and shifts to higher BE. The valence band spectrum for YbCrSb{sub 3} also supports the presence of divalent ytterbium. - Graphical Abstract: In their valence band spectra, the 4f-band intensifies and shifts to higher BE on progressing from LaCrSb{sub 3} to NdCrSb{sub 3}. Highlights: Black-Right-Pointing-Pointer High-resolution core-line and valence band XPS spectra were measured for RECrSb{sub 3}. Black-Right-Pointing-Pointer Divalent Yb is present in YbCrSb{sub 3}, in contrast to trivalent RE in other members. Black-Right-Pointing-Pointer Asymmetric Cr 2p spectral lineshape confirms delocalization of Cr valence electrons. Black-Right-Pointing-Pointer Small negative Sb 3d BE shifts support assignment of

  1. XPS investigation on vacuum thermal desorption of UV/ozone treated GaAs(100) surfaces

    NASA Astrophysics Data System (ADS)

    Cossu, G.; Ingo, G. M.; Mattogno, G.; Padeletti, G.; Proietti, G. M.

    In order to prepare suitable surfaces for molecular beam epitaxy (MBE), sacrificial thin oxide layers on HCl etched GaAs(100) surfaces were grown by both air and UV/ozone exposure. Passive films were subsequently removed by vacuum thermal desorption to achieve surfaces that were smooth and clean on an atomic scale. The evolution of the surface chemical composition, as a function of vacuum desorption temperature, has been studied by means of X-ray photoelectron spectroscopy (XPS). XPS results have evidenced for air and UV/ozone exposed GaAs(100) surfaces a relationship between desorption temperature and surface chemical composition; indeed, the oxide removal is temperature dependent and sequentially selective as follows: As 2O 3. AsO and Ga 2O 3. Furthermore, XPS results have shown that air-grown films have a chemical composition and thermal desorption behaviour different from UV/ozone treated materials. Indeed, these latter have an As 2O 3/Ga 2O 3 and an unoxidized As/Ga ratio close to unity for as grown and thermal treated at 580°C surfaces, respectively. By contrast, air-exposed GaAs(100) materials are Ga 2O 3-enriched and after vacuum thermal desorption treatments have never a stoichiometric composition(As (GaAs)/Ga (GaAs)= 1). Furthermore UV/ozone treated GaAs(100) surfaces subjected to a vacuum thermal treatment at 580°C, have a troublesome organic contamination level below XPS detectability, whereas from air-exposed surfaces, carbon is not completely thermally removable

  2. Fluorescence, XPS, and TOF-SIMS surface chemical state image analysis of DNA microarrays.

    PubMed

    Lee, Chi-Ying; Harbers, Gregory M; Grainger, David W; Gamble, Lara J; Castner, David G

    2007-08-01

    Performance improvements in DNA-modified surfaces required for microarray and biosensor applications rely on improved capabilities to accurately characterize the chemistry and structure of immobilized DNA molecules on micropatterned surfaces. Recent innovations in imaging X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) now permit more detailed studies of micropatterned surfaces. We have exploited the complementary information provided by imaging XPS and imaging TOF-SIMS to detail the chemical composition, spatial distribution, and hybridization efficiency of amine-terminated single-stranded DNA (ssDNA) bound to commercial polyacrylamide-based, amine-reactive microarray slides, immobilized in both macrospot and microarray diagnostic formats. Combinations of XPS imaging and small spot analysis were used to identify micropatterned DNA spots within printed DNA arrays on slide surfaces and quantify DNA elements within individual microarray spots for determination of probe immobilization and hybridization efficiencies. This represents the first report of imaging XPS of DNA immobilization and hybridization efficiencies for arrays fabricated on commercial microarray slides. Imaging TOF-SIMS provided distinct analytical data on the lateral distribution of DNA within single array microspots before and after target hybridization. Principal component analysis (PCA) applied to TOF-SIMS imaging datasets demonstrated that the combination of these two techniques provides information not readily observable in TOF-SIMS images alone, particularly in identifying species associated with array spot nonuniformities (e.g., "halo" or "donut" effects often observed in fluorescence images). Chemically specific spot images were compared to conventional fluorescence scanned images in microarrays to provide new information on spot-to-spot DNA variations that affect current diagnostic reliability, assay variance, and sensitivity.

  3. Fluorescence, XPS, and TOF-SIMS surface chemical state image analysis of DNA microarrays.

    PubMed

    Lee, Chi-Ying; Harbers, Gregory M; Grainger, David W; Gamble, Lara J; Castner, David G

    2007-08-01

    Performance improvements in DNA-modified surfaces required for microarray and biosensor applications rely on improved capabilities to accurately characterize the chemistry and structure of immobilized DNA molecules on micropatterned surfaces. Recent innovations in imaging X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) now permit more detailed studies of micropatterned surfaces. We have exploited the complementary information provided by imaging XPS and imaging TOF-SIMS to detail the chemical composition, spatial distribution, and hybridization efficiency of amine-terminated single-stranded DNA (ssDNA) bound to commercial polyacrylamide-based, amine-reactive microarray slides, immobilized in both macrospot and microarray diagnostic formats. Combinations of XPS imaging and small spot analysis were used to identify micropatterned DNA spots within printed DNA arrays on slide surfaces and quantify DNA elements within individual microarray spots for determination of probe immobilization and hybridization efficiencies. This represents the first report of imaging XPS of DNA immobilization and hybridization efficiencies for arrays fabricated on commercial microarray slides. Imaging TOF-SIMS provided distinct analytical data on the lateral distribution of DNA within single array microspots before and after target hybridization. Principal component analysis (PCA) applied to TOF-SIMS imaging datasets demonstrated that the combination of these two techniques provides information not readily observable in TOF-SIMS images alone, particularly in identifying species associated with array spot nonuniformities (e.g., "halo" or "donut" effects often observed in fluorescence images). Chemically specific spot images were compared to conventional fluorescence scanned images in microarrays to provide new information on spot-to-spot DNA variations that affect current diagnostic reliability, assay variance, and sensitivity. PMID:17625851

  4. X-ray photoelectron and mass spectroscopic study of electron irradiation and thermal stability of polytetrafluoroethylene

    NASA Technical Reports Server (NTRS)

    Wheeler, Donald R.; Pepper, Stephen V.

    1990-01-01

    Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. A quantitative comparison of the radiation dose rate with that in other reported studies showed that, for a given total dose, the damage observed by XPS is greater for higher dose rates. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS that were associated with damage diminished, giving the appearance that the radiation damage annealed. The apparent annealing of the radiation damage was found to be due to the covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

  5. An in situ x-ray photoelectron spectroscopy study of the initial stages of rf magnetron sputter deposition of indium tin oxide on p-type Si substrate

    SciTech Connect

    Rein, M. H.; Holt, A. O.; Hohmann, M. V.; Klein, A.; Thogersen, A.; Mayandi, J.; Monakhov, E. V.

    2013-01-14

    The interface between indium tin oxide and p-type silicon is studied by in situ X-ray photoelectron spectroscopy (XPS). This is done by performing XPS without breaking vacuum after deposition of ultrathin layers in sequences. Elemental tin and indium are shown to be present at the interface, both after 2 and 10 s of deposition. In addition, the silicon oxide layer at the interface is shown to be composed of mainly silicon suboxides rather than silicon dioxide.

  6. Laboratory simulations of photoelectron sheaths

    NASA Astrophysics Data System (ADS)

    Dove, A.; Wang, X.; Robertson, S. H.; Poppe, A.; Horanyi, M.

    2011-12-01

    Surfaces of airless natural bodies, such as the Moon and asteroids, and spacecraft in space are exposed to solar ultraviolet radiation that creates a photoelectron sheath that dominates the near-surface plasma environment. In order to reproduce and investigate this photoelectron layer, we conduct experiments in vacuum with Xe excimer lamps that emit UV light at ~172 nm (7.21 eV) which is of sufficient intensity to create a photoelectron layer with a characteristic length on the order of several centimeters. We utilize surfaces, such as Zr and CeO2 that have a low work function and a high photoelectron emission yield to maximize the electron density. In order to repel stray electrons that are produced by other surfaces in the chamber, and to define a reference potential, a negatively biased grid is placed 7.5 cm above the surface. The surface and the grid are used as a retarding potential analyzer to determine the energy distribution of the electrons emitted from the surface. When the grid is biased to -20 V, the emitted electrons have an approximately Maxwellian energy distribution with a characteristic temperature of 1.4 ± 0.3 eV. A Langmuir probe is also used as a diagnostic tool to find the effective electron temperature and electron density within the pure electron plasma, and is moved in order to probe different heights above the surface. The derived densities and potentials are compared with those predicted by 1-D PIC code simulations.

  7. [The Application of X-Ray Photoelectron Spectroscopy on Refining Catalyst].

    PubMed

    Qiu, Li-mei; Xu, Guang-tong

    2015-12-01

    Abstract XPS analysis provides qualitative, quantitative and chemical state information for surface elements of solid materials. Therefore, XPS is widely applied in the characterization of refining catalyst. In the present paper, the applications of XPS in the field of typical refining catalysts, including hydrogenation catalyst, S Zorb sorbent and rare-earth modified Y zeolite, are illustrated and exemplified. For sulfided Co (Ni)-Mo (W)/Al₂O₃(-SiO₂) hydrodesulfurization catalysts, the anhydrous oxygen-free transfer process from the reactor to XPS chamber was illustrated. The identification and peak fitting of S(2p) , Mo(3d), W (4f), Co(2p) and Ni(2p) XPS spectra were summarized. The typical chemical states of the active elements were described. Based on these results, the sulfidation extents of the active metals and the cause for the sulfidation inadequency of the catalysts were deduced. As for the application of XPS in S Zorb sorbent, the existence form of zinc was obtained from ZnLMM Auger spectra, and the fracture mechanism and deactivation reason of the sorbent were derived. The distribution of sulfur along the vertical direction was investigated using XPS and argon ion sputtering XPS. Besides, in situ XPS was applied to study the conversion of sulfur- and nickel-containing species for spent sorbent under hydrogen condition. Finally, for cerium modified Y zeolite, the location of cerium ion inside and outside Y zeolite cage was investigated. The results indicate that the liquid phase method is more suitable for the migration of cerium ion toward zeolite as compared with the solid phase method. PMID:26964241

  8. The electron spectro-microscopy beamline at National Synchrotron Light Source II: A wide photon energy range, micro-focusing beamlinefor photoelectron spectro-microscopies

    SciTech Connect

    Reininger R.; Hulbert L.; Johnson P.D.; Sadowski, J.T.; Starr, D.E.; Chubar, O.; Valla, T.; Vescovo, E.

    2012-02-13

    A comprehensive optical design for a high-resolution, high-flux, wide-energy range, micro-focused beamline working in the vacuum ultraviolet and soft x-ray photon energy range is proposed. The beamline is to provide monochromatic radiation to three photoelectron microscopes: a full-field x-ray photoelectron emission microscope and two scanning instruments, one dedicated to angle resolved photoemission spectroscopy ({micro}-ARPES) and one for ambient pressure x-ray photoelectron spectroscopy and scanning photoelectron microscopy (AP-XPS/SPEM). Microfocusing is achieved with state of the art elliptical cylinders, obtaining a spot size of 1 {micro}m for ARPES and 0.5 {micro}m for AP-XPS/SPEM. A detailed ray tracing analysis quantitatively evaluates the overall beamline performances.

  9. The electron spectro-microscopy beamline at National Synchrotron Light Source II: A wide photon energy range, micro-focusing beamline for photoelectron spectro-microscopies

    SciTech Connect

    Reininger, R.; Hulbert, S. L.; Chubar, O.; Vescovo, E.; Johnson, P. D.; Valla, T.; Sadowski, J. T.; Starr, D. E.

    2012-02-15

    A comprehensive optical design for a high-resolution, high-flux, wide-energy range, micro-focused beamline working in the vacuum ultraviolet and soft x-ray photon energy range is proposed. The beamline is to provide monochromatic radiation to three photoelectron microscopes: a full-field x-ray photoelectron emission microscope and two scanning instruments, one dedicated to angle resolved photoemission spectroscopy ({mu}-ARPES) and one for ambient pressure x-ray photoelectron spectroscopy and scanning photoelectron microscopy (AP-XPS/SPEM). Microfocusing is achieved with state of the art elliptical cylinders, obtaining a spot size of 1 {mu}m for ARPES and 0.5 {mu}m for AP-XPS/SPEM. A detailed ray tracing analysis quantitatively evaluates the overall beamline performances.

  10. X-ray Photoelectron Spectroscopy of Pyridinium-Based Ionic Liquids: Comparison to Imidazolium- and Pyrrolidinium-Based Analogues.

    PubMed

    Men, Shuang; Mitchell, Daniel S; Lovelock, Kevin R J; Licence, Peter

    2015-07-20

    We investigate eight 1-alkylpyridinium-based ionic liquids of the form [Cn Py][A] by using X-ray photoelectron spectroscopy (XPS). The electronic environment of each element of the ionic liquids is analyzed. In particular, a reliable fitting model is developed for the C 1s region that applies to each of the ionic liquids. This model allows the accurate charge correction of binding energies and the determination of reliable and reproducible binding energies for each ionic liquid. Shake-up/off phenomena are determinedfor both C 1s and N 1s spectra. The electronic interaction between cations and anions is investigated for both simple ionic liquids and an example of an ionic-liquid mixture; the effect of the anion on the electronic environment of the cation is also explored. Throughout the study, a detailed comparison is made between [C8 Py][A] and analogues including 1-octyl-1-methylpyrrolidinium- ([C8 C1 Pyrr][A]), and 1-octyl-3-methylimidazolium- ([C8 C1 Im][A]) based samples, where X is common to all ionic liquids.

  11. Photoelectron spectroscopy study of AlN films grown on n-type 6H-SiC by MOCVD

    NASA Astrophysics Data System (ADS)

    Liang, F.; Chen, P.; Zhao, D. G.; Jiang, D. S.; Zhao, Z. J.; Liu, Z. S.; Zhu, J. J.; Yang, J.; Liu, W.; He, X. G.; Li, X. J.; Li, X.; Liu, S. T.; Yang, H.; Liu, J. P.; Zhang, L. Q.; Zhang, Y. T.; Du, G. T.

    2016-09-01

    Photoelectron spectroscopy has been employed to analyze the content and chemical states of the elements on the surface of AlN films with different thickness, which are synthesized by metalorganic chemical vapor deposition on the n-type SiC substrates under low pressure. It is found that, besides the carbon and gallium on the AlN surface, the atom percentage of surface oxygen increases from 4.9 to 8.4, and the electron affinity also increases from 0.36 to 0.97 eV, when the thickness of AlN films increase from 50 to 400 nm. Furthermore, accompanying with the high-resolution XPS spectra of the O 1s, it is speculated that surface oxygen may be the major influence on the electron affinity, where the surface oxygen changes the surface chemical states through replacing N to form Al-O bond and Ga-O bond, although there are also a few of Ga and C contaminations in the chemical sate of Ga-O and C-C, respectively.

  12. Dissolution of uranophane: An AFM, XPS, SEM and ICP study

    NASA Astrophysics Data System (ADS)

    Schindler, Michael; Freund, Michael; Hawthorne, Frank C.; Burns, Peter C.; Maurice, Patricia A.

    2009-05-01

    Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H 2O) 5[(UO 2)(SiO 3(OH)] 2, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb 2+-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl 2-HCl solution of pH 2. They are part of an aged silica coating of composition Si 2O 2(OH) 4(H 2O) n. An amorphous layer forms on the surface of uranophane in a MgCl 2-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO 3) 2-HCl and BaCl 2-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders

  13. XPS study of the Al/SiO2 interface viewed from the SiO2 side

    NASA Technical Reports Server (NTRS)

    Hecht, M. H.; Grunthaner, F. J.; Maserjian, J.

    1984-01-01

    The first nondestructive measurement of the chemical and physical characteristics of the interface between bulk SiO2 and thick aluminum films is presented. Both X-ray photoelectron spectroscopy (XPS) and electrical measurements of unannealed resistively evaporated Al films on thermal SiO2 indicate an atomically abrupt interface. Postmetallization annealing (PMA) at 450 C induces reduction of the SiO2 by the aluminum, resulting in the layer ordering SiO2/Al2O3/Si/Al. The XPS measurement is performed from the SiO2 side after removal of the Si substrate after etching with XeF2 gas and thinning of the SiO2 layer with HF:ETOH. This represents a powerful new approach to the study of metal-insulator and other interfaces.

  14. Location and Visualization of Working p-n and/or n-p Junctions by XPS

    PubMed Central

    Copuroglu, Mehmet; Caliskan, Deniz; Sezen, Hikmet; Ozbay, Ekmel; Suzer, Sefik

    2016-01-01

    X-ray photoelectron spectroscopy (XPS) is used to follow some of the electrical properties of a segmented silicon photodetector, fabricated in a p-n-p configuration, during operation under various biasing configurations. Mapping of the binding energy position of Si2p reveals the shift in the position of the junctions with respect to the polarity of the DC bias applied. Use of squared and triangular shaped wave excitations, while recording XPS data, allows tapping different electrical properties of the device under normal operational conditions, as well as after exposing parts of it to harsh physical and chemical treatments. Unique and chemically specific electrical information can be gained with this noninvasive approach which can be useful especially for localized device characterization and failure analyses. PMID:27582318

  15. Polymer coatings on conductive polypyrroles surface characterization by XPS, ToFSIMS, inverse gas chromatography and AFM

    SciTech Connect

    Chehimi, M.M.; Abel, M.; Delamar, M.; Watts, J.F.; Zhdan, P.A.

    1996-01-01

    The study of PMMA adsorption on some conducting polypyrroles (PPys) using a variety of surface analytical techniques is reported. PMMA adsorption was monitored by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF-SIMS) and inverse gas chromatography (IGC). XPS and ToF-SIMS permit to determine the surface composition of PMMA-coated PPy surfaces vs the solvent nature, temperature and the PPy dopant anion. Both techniques show that acid-base interactions may govern PMMA adsorption. IGC was used to determine the coating morphology by monitoring the surface energy of the coated PPy powders. It is suggested that homogeneity of PMMA coatings increases with decreasing solvent power. Preliminary atomic force microscopy (AFM) results on PMMA films cast on flat PPy surfaces confirm the IGC observation. {copyright} {ital 1996 American Institute of Physics.}

  16. Location and Visualization of Working p-n and/or n-p Junctions by XPS.

    PubMed

    Copuroglu, Mehmet; Caliskan, Deniz; Sezen, Hikmet; Ozbay, Ekmel; Suzer, Sefik

    2016-01-01

    X-ray photoelectron spectroscopy (XPS) is used to follow some of the electrical properties of a segmented silicon photodetector, fabricated in a p-n-p configuration, during operation under various biasing configurations. Mapping of the binding energy position of Si2p reveals the shift in the position of the junctions with respect to the polarity of the DC bias applied. Use of squared and triangular shaped wave excitations, while recording XPS data, allows tapping different electrical properties of the device under normal operational conditions, as well as after exposing parts of it to harsh physical and chemical treatments. Unique and chemically specific electrical information can be gained with this noninvasive approach which can be useful especially for localized device characterization and failure analyses. PMID:27582318

  17. Location and Visualization of Working p-n and/or n-p Junctions by XPS

    NASA Astrophysics Data System (ADS)

    Copuroglu, Mehmet; Caliskan, Deniz; Sezen, Hikmet; Ozbay, Ekmel; Suzer, Sefik

    2016-09-01

    X-ray photoelectron spectroscopy (XPS) is used to follow some of the electrical properties of a segmented silicon photodetector, fabricated in a p-n-p configuration, during operation under various biasing configurations. Mapping of the binding energy position of Si2p reveals the shift in the position of the junctions with respect to the polarity of the DC bias applied. Use of squared and triangular shaped wave excitations, while recording XPS data, allows tapping different electrical properties of the device under normal operational conditions, as well as after exposing parts of it to harsh physical and chemical treatments. Unique and chemically specific electrical information can be gained with this noninvasive approach which can be useful especially for localized device characterization and failure analyses.

  18. C K-edge NEXAFS spectra of graphene with physical and chemical defects: a study based on density functional theory.

    PubMed

    Ehlert, Christopher; Unger, Wolfgang E S; Saalfrank, Peter

    2014-07-21

    Recently, C K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of graphite (HOPG) surfaces have been measured for the pristine material, and for HOPG treated with either bromine or krypton plasmas (Lippitz et al., Surf. Sci., 2013, 611, L1). Changes of the NEXAFS spectra characteristic for physical (krypton) and/or chemical/physical modifications of the surface (bromine) upon plasma treatment were observed. Their molecular origin, however, remained elusive. In this work we study by density functional theory, the effects of selected point and line defects as well as chemical modifications on NEXAFS carbon K-edge spectra of single graphene layers. For Br-treated surfaces, also Br 3d X-ray Photoelectron Spectra (XPS) are simulated by a cluster approach, to identify possible chemical modifications. We observe that some of the defects related to plasma treatment lead to characteristic changes of NEXAFS spectra, similar to those in experiment. Theory provides possible microscopic origins for these changes. PMID:24901898

  19. RECENT XPS STUDIES OF THE EFFECT OF PROCESSING ON NB SRF SURFACES

    SciTech Connect

    Hui Tian; Binping Xiao; Michael Kelley; Charles Reece; A. Demasi; L. Pipe; Kevin Smith

    2008-02-12

    XPS studies have consistently shown that Nb surfaces for SRF chiefly comprise of a few nm of Nb2O5 on top of Nb metal, with minor amounts of Nb sub-oxides. Nb samples after BCP/EP treatment with post-baking at the various conditions have been examined by using synchrotron based XPS. Despite the confounding influence of surface roughness, certain outcomes are clear. Lower-valence Nb species are always and only associated with the metal/oxide interface, but evidence for an explicit layer structure or discrete phases is lacking. Post-baking without air exposure shows decreased oxide layer thickness and increased contribution from lower valence species, but spectra obtained after subsequent air exposure cannot be distinguished from those obtained prior to baking, though the SRF performance improvement remains.

  20. Study of gadolinia-doped ceria solid electrolyte surface by XPS

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

    Gadolinia-doped ceria (CGO) is an important material to be used as electrolyte for solid oxide fuel cell for intermediate temperature operation. Ceria doped with 10 mol% gadolinia (Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}) was prepared by conventional solid state synthesis and found to be single phase by room temperature X-ray diffraction (XRD). The chemical states of the surface of the prepared sample were analyzed by X-ray photoelectron spectroscopy (XPS). Though Gd was present in its characteristic chemical state, Ce was found in both Ce{sup 4+} and Ce{sup 3+} states. Presence of Ce{sup 3+} state was ascribed to the differential yield of oxygen atoms in the sputtering process.

  1. XPS/STM study of model bimetallic Pd-Au/HOPG catalysts

    NASA Astrophysics Data System (ADS)

    Bukhtiyarov, Andrey V.; Prosvirin, Igor P.; Bukhtiyarov, Valerii I.

    2016-03-01

    The preparation of model bimetallic Pd-Au/HOPG catalysts has been investigated using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) techniques. Initially, model "core-shell" type Pd-Au/HOPG catalysts with similar particle size distribution (5-8 nm), but with different densities of particle locations on the HOPG surface and Pd/Au atomic ratios are prepared. Further, their thermal stability is studied within a temperature range of 50-500 °C at UHV conditions. It has been shown that annealing the model catalysts at a temperature range of 300-400 °C leads to formation of Pd-Au alloyed particles. Enhancement of heating temperature up to 500 °C results in sintering of bimetallic nanoparticles. Contribution of different parameters controlling the properties of Pd-Au alloyed particles has been discussed.

  2. Imaging electron dynamics with time- and angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Popova-Gorelova, Daria; Küpper, Jochen; Santra, Robin

    2016-07-01

    We theoretically study how time- and angle-resolved photoemission spectroscopy can be applied for imaging coherent electron dynamics in molecules. We consider a process in which a pump pulse triggers coherent electronic dynamics in a molecule by creating a valence electron hole. An ultrashort extreme ultraviolet probe pulse creates a second electron hole in the molecule. Information about the electron dynamics is accessed by analyzing angular distributions of photoemission probabilities at a fixed photoelectron energy. We demonstrate that a rigorous theoretical analysis, which takes into account the indistinguishability of transitions induced by the ultrashort, broadband probe pulse and electron hole correlation effects, is necessary for the interpretation of time- and angle-resolved photoelectron spectra. We show how a Fourier analysis of time- and angle-resolved photoelectron spectra from a molecule can be applied to follow its electron dynamics by considering photoelectron distributions from an indole molecular cation with coherent electron dynamics.

  3. High temperature and high resolution uv photoelectron spectroscopy using supersonic molecular beams

    SciTech Connect

    Wang, Lai-Sheng; Reutt-Robey, J.E.; Niu, B.; Lee, Y.T.; Shirley, D.A.; Maryland Univ., College Park, MD . Dept. of Chemistry and Biochemistry; Lawrence Berkeley Lab., CA )

    1989-07-01

    A high temperature molecular beam source with electron bombardment heating has been built for high resolution photoelectron spectroscopic studies of high temperature species and clusters. This source has the advantages of: producing an intense, continuous, seeded molecular beam, eliminating the interference of the heating mechanism from the photoelectron measurement. Coupling the source with our hemispherical electron energy analyzer, we can obtain very high resolution HeI{alpha} (584{angstrom}) photoelectron spectra of high temperature species. Vibrationally-resolved photoelectron spectra of PbSe, As{sub 2}, As{sub 4}, and ZnCl{sub 2} are shown to demonstrate the performance of the new source. 25 refs., 8 figs., 1 tab.

  4. XPS study of Al/polyethylene terephtalate interface

    NASA Astrophysics Data System (ADS)

    Silvain, J. F.; Arzur, A.; Alnot, M.; Ehrhardt, J. J.; Lutgen, P.

    1991-07-01

    X-ray photoelectron spectroscopy has been used to study the formation of the aluminium/polyethylene terephtalate (Al/PET) interface. On control PET, C ls and O ls exhibits the usual behavior of the PET. An extra Cvls appears on Ar+ -bombarded PET whilst the CIV 1s component is decreased by about 10% compared to the control PET. On fluorine-treated PET, the C ls spectra have been decomposed into six different components. After annealing at 500 K, the C ls shows the usual behavior of the PET indicative of a decrease of the fluorine concentration in the polymer surface. Al films up to 64 Å were evaporated with a Knudsen cell. The Al/PET interface exhibits the behavior of the layer by layer growth. A preferential aluminum bonding with PET is observed for CIV1s. The Al evaporated onto PET presents a complex A12p peak decomposed into Almetal and aloxide component. The ratio Almetal/Aloxide changes with the PET and the temperature of the PET during Al deposition. Transmission electron microscopy (TEM) is performed in order to correlate the morphology and the adhesion of the Al film on PET.

  5. The chemical state of arsenic in minerals of environmental interest--an XPS and an XAES study.

    PubMed

    Atzei, Davide; Da Pelo, Stefania; Elsener, Bernhard; Fantauzzi, Marzia; Frau, Franco; Pierfranco, Lattanzi; Rossi, Antonella

    2003-01-01

    A systematic analytical study using X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) has been carried out to characterize the chemical state of arsenic in complex environmental samples. The conventional approach, which relies on the chemical shift of the core levels As3d, provides ambiguous results in determining the chemical environment of arsenic. A more accurate approach, based on the Auger parameter and on the Wagner (Chemical State) plot, which combines AsLMM kinetic energy and As3d binding energy, was adopted. This novel method for determining the chemical state of arsenic was employed to completely characterize arsenic in complex environmental samples.

  6. Solar Ion Processing of Major Element Surface Compositions of Mature Mare Soils: Insights from Combined XPS and Analytical TEM Observations

    NASA Technical Reports Server (NTRS)

    Christoffersen, R.; Dukes, C.; Keller, L. P.; Baragiola, R.

    2012-01-01

    Solar wind ions are capable of altering the sur-face chemistry of the lunar regolith by a number of mechanisms including preferential sputtering, radiation-enhanced diffusion and sputter erosion of space weathered surfaces containing pre-existing compositional profiles. We have previously reported in-situ ion irradiation experiments supported by X-ray photoelectron spectroscopy (XPS) and analytical TEM that show how solar ions potentially drive Fe and Ti reduction at the monolayer scale as well as the 10-100 nm depth scale in lunar soils [1]. Here we report experimental data on the effect of ion irradiation on the major element surface composition in a mature mare soil.

  7. Arsenopyrite and pyrite bioleaching: evidence from XPS, XRD and ICP techniques.

    PubMed

    Fantauzzi, Marzia; Licheri, Cristina; Atzei, Davide; Loi, Giovanni; Elsener, Bernhard; Rossi, Giovanni; Rossi, Antonella

    2011-10-01

    In this work, a multi-technical bulk and surface analytical approach was used to investigate the bioleaching of a pyrite and arsenopyrite flotation concentrate with a mixed microflora mainly consisting of Acidithiobacillus ferrooxidans. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy mineral surfaces investigations, along with inductively coupled plasma-atomic emission spectroscopy and carbon, hydrogen, nitrogen and sulphur determination (CHNS) analyses, were carried out prior and after bioleaching. The flotation concentrate was a mixture of pyrite (FeS(2)) and arsenopyrite (FeAsS); after bioleaching, 95% of the initial content of pyrite and 85% of arsenopyrite were dissolved. The chemical state of the main elements (Fe, As and S) at the surface of the bioreactor feed particles and of the residue after bioleaching was investigated by X-ray photoelectron and X-ray excited Auger electron spectroscopy. After bioleaching, no signals of iron, arsenic and sulphur originating from pyrite and arsenopyrite were detected, confirming a strong oxidation and the dissolution of the particles. On the surfaces of the mineral residue particles, elemental sulphur as reaction intermediate of the leaching process and precipitated secondary phases (Fe-OOH and jarosite), together with adsorbed arsenates, was detected. Evidence of microbial cells adhesion at mineral surfaces was also produced: carbon and nitrogen were revealed by CHNS, and nitrogen was also detected on the bioleached surfaces by XPS. This was attributed to the deposition, on the mineral surfaces, of the remnants of a bio-film consisting of an extra-cellular polymer layer that had favoured the bacterial action.

  8. Surface Coordination of Adatoms by Scanned Low Energy Photoelectron Diffraction

    NASA Astrophysics Data System (ADS)

    Asensio, M. C.

    In this article, a brief overview of the current activity in the field of low energy photoelectron diffraction is presented. Although alternatively angle and energy-scanned photoelectron diffraction can be used to obtain the surface-structural information, we limit our discussion to the low energy and energy-scanned modes and their use in connection with a new developed direct method. By the use of this most recent approach, adatom-substrate distances and adsorption sites are directly revealed from a discrete mapping of the Fourier transform of scanned energy photoelectron diffraction spectra, measured at a representative set of geometries, which depend on the symmetry of the particular studied system. In addition, a short discussion on the determination of the detailed structure of adsorbed overlayers by the traditional trial-and-error method is included, using model multiple scattering calculations. These latest developments are illustrated with a specific example of an atomic adsorbate, and comments about the capabilities and limitations of photoelectron diffraction as a structural technique in new fields.

  9. An XPS analytical approach for elucidating the microbially mediated enargite oxidative dissolution.

    PubMed

    Fantauzzi, M; Rossi, G; Elsener, B; Loi, G; Atzei, D; Rossi, A

    2009-04-01

    In this work, the microbe-mediated oxidative dissolution of enargite surfaces (Cu(3)AsS(4)) was studied on powdered samples exposed to 9K nutrient solution (pH 2.3) inoculated by Acidithiobacillus ferrooxidans initially adapted to arsenopyrite. These conditions simulate the acid mine environment. The redox potential of the inoculated solutions increased up to +0.72 V vs normal hydrogen electrode (NHE), indicating the increase of the Fe(3+) to Fe(2+) ratio, and correspondingly the pH decreased to values as low as 1.9. In the sterile 9K control, the redox potential and pH remained constant at +0.52 V NHE and 2.34, respectively. Solution analyses showed that in inoculated medium Cu and As dissolved stoichiometrically with a dissolution rate of about three to five times higher compared to the sterile control. For the first time, X-ray photoelectron spectroscopy (XPS) was carried out on the bioleached enargite powder with the aim of clarifying the role of the microorganisms in the dissolution process. XPS results provide evidence of the formation of a thin oxidized layer on the mineral surface. Nitrogen was also detected on the bioleached surfaces and was attributed to the presence of an extracellular polymer substance layer supporting a mechanism of bacteria attachment via the formation of a biofilm a few nanometers thick, commonly known as nanobiofilm.

  10. Investigation of damaged interior walls using synchrotron-based XPS and XANES.

    PubMed

    Poo-arporn, Yingyot; Thachepan, Surachai; Palangsuntikul, Rungtiva

    2015-01-01

    Evidence of internal sulfate attack in field exposure was demonstrated by the damaged interior wall of a three-year-old house situated in Nakhon Ratchasima Province, Thailand. Partial distension of the mortar was clearly observed together with an expansion of a black substance. Removal of the black substance revealed a dense black layer. This layer was only found in the vicinity of the damaged area, suggesting that this black material is possibly involved in the wall cracking. By employing synchrotron-based X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) techniques, the unknown sample was chemically identified. The S 2p and O 1s XPS results mutually indicated the existence of sulfate species in the materials collected from the damaged area. The XANES results indicated the presence of ferrous (II) sulfate, confirming sulfate-induced expansion and cracking. The sulfate attack in the present case appeared to physically affect the structure whereas the chemical integrity at the molecular level of the calcium silicate hydrate phase was retained since there was a lack of spectroscopic evidence for calcium sulfate. It was speculated that internal sulfate probably originated from the contaminated aggregates used during the construction. The current findings would be beneficial for understanding the sulfate-attack mechanism as well as for future prevention against sulfate attack during construction.

  11. XAS and XPS Characterization of Mercury Binding on Brominated Activated Carbon

    SciTech Connect

    Hutson,N.; Attwood, B.; Scheckel, K.

    2007-01-01

    Brominated powdered activated carbon sorbents have been shown to be quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when burning Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) have been used to determine information about the speciation and binding of mercury on two commercially available brominated activated carbons. The results are compared with similar analysis of a conventional (non-halogenated) and chlorinated activated carbon. Both the XAS and XPS results indicate that the mercury, though introduced as elemental vapor, is consistently bound on the carbon in the oxidized form. The conventional and chlorinated activated carbons appeared to contain mercury bound to chlorinated sites and possibly to sulfate species that have been incorporated onto the carbon from adsorbed SO{sub 2}. The mercury-containing brominated sorbents appear to contain mercury bound primarily at bromination sites. The mechanism of capture for the sorbents likely consists of surface-enhanced oxidation of the elemental mercury vapor via interaction with surface-bound halide species with subsequent binding by surface halide or sulfate species.

  12. XAS and XPS characterization of mercury binding on brominated activated carbon

    SciTech Connect

    Nick D. Hutson; Brian C. Attwood; Kirk G. Scheckel

    2007-03-01

    Brominated powdered activated carbon sorbents have been shown to be quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when burning Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) have been used to determine information about the speciation and binding of mercury on two commercially available brominated activated carbons. The results are compared with similar analysis of a conventional (non-halogenated) and chlorinated activated carbon. Both the XAS and XPS results indicate that the mercury, though introduced as elemental vapor, is consistently bound on the carbon in the oxidized form. The conventional and chlorinated activated carbons appeared to contain mercury bound to chlorinated sites and possibly to sulfate species that have been incorporated onto the carbon from adsorbed SO{sub 2}. The mercury-containing brominated sorbents appear to contain mercury bound primarily at bromination sites. The mechanism of capture for the sorbents likely consists of surface-enhanced oxidation of the elemental mercury vapor via interaction with surface-bound halide species with subsequent binding by surface halide or sulfate species. 22 refs., 3 figs., 2 tabs.

  13. [XPS study on the influence of calcination conditions to cerium ion valence].

    PubMed

    Mei, Yan; Yan, Jian-ping; Nie, Zuo-ren

    2010-01-01

    For the system of Ce(NO3)2.6H2O and urea solution during homogeneous precipitation method, X-ray diffraction (XRD), infrared spectrum (IR) and especially X-ray photoelectron spectroscopy (XPS) were used to study and characterize the product structure, variety of cerium ion valence, compound surface character and kernel electronic configurations. The results of XRD and IR showed that calcination temperature had a great effect on the cerium ion valence. The products are orthorhombic Ce2 O(CO3)2.H2O with valence III by using homogeneous precipitation method directly. When heated from the temperature 200 degrees C to 250 degrees C, the product of CeO(CO3)2.H2O with valence VI was finally changed into stable CeO2 with valence IV. XPS was used to study the surface character and kernel electronic configurations of the three different compounds through fine scanning of O(1s), Ce(3d) and Ce(4d) apices, and the results approved that the compounds with different valences are caused by the different valence electronic configurations of the products.

  14. XPS characterization scheme for phase-pure epitaxial NbO2

    NASA Astrophysics Data System (ADS)

    Hadamek, Tobias; Posadas, Agham; Demkov, Alex

    NbO2 shows a semiconductor-to-metal transition with an associated structural transition of Peierls type. NbO2 and Nb2O5 or mixtures thereof have also shown electrically induced insulator-to-metal transitions. To shed light on the nature of the electrically induced insulator-to-metal transition it is important to grow high phase purity NbO2 and Nb2O5 and compare electrical measurements with mixed niobium oxides and with different electrode materials. Processing NbO2 and avoiding surface oxidation requires ultra-high vacuum (UHV) conditions. Niobium oxide thin films where grown in UHV by molecular beam epitaxy on 111-oriented STO substrates and analyzed by X-ray photoelectron spectroscopy (XPS). It was shown that the NbO2 3d core level spectrum exhibits an asymmetric spin-orbit peak pair with more spectral weight on the high binding energy side. Based on the shape of the Nb 3d core levels, peak positions relative to the oxygen O 1s peak, and the valence band shape and height ratio of the niobium 4dxy split-off band to the oxygen 2p band, an identification scheme for NbO2 by XPS was devised. Complementary the NbO2 phase was confirmed by reflection high-energy electron and x-ray diffraction analysis.

  15. XPS study on the use of 3-aminopropyltriethoxysilane to bond chitosan to a titanium surface.

    PubMed

    Martin, Holly J; Schulz, Kirk H; Bumgardner, Joel D; Walters, Keisha B

    2007-06-01

    Chitosan, a biopolymer found in the exoskeletons of shellfish, has been shown to be antibacterial, biodegradable, osteoconductive, and has the ability to promote organized bone formation. These properties make chitosan an ideal material for use as a bioactive coating on medical implant materials. In this study, coatings made from 86.4% de-acetylated chitosan were bound to implant-quality titanium. The chitosan films were bound through a three-step process that involved the deposition of 3-aminopropyltriethoxysilane (APTES) in toluene, followed by a reaction between the amine end of APTES with gluteraldehyde, and finally, a reaction between the aldehyde end of gluteraldehyde and chitosan. Two different metal treatments were examined to determine if major differences in the ability to bind chitosan could be seen. X-ray photoelectron spectroscopy (XPS) was used to examine the surface of the titanium metal and to study the individual reaction steps. The changes to the titanium surface were consistent with the anticipated reaction steps, with significant changes in the amounts of nitrogen, silicon, and titanium that were present. It was demonstrated that more APTES was bound to the piranha-treated titanium surface as compared to the passivated titanium surface, based on the amounts of titanium, carbon, nitrogen, and silicon that were present. The metal treatments did not affect the chemistry of the chitosan films. Using toluene to bond APTES on titanium surfaces, rather than aqueous solutions, prevented the formation of unwanted polysiloxanes and increased the amount of silane on the surface for forming bonds to the chitosan films. Qualitatively, the films were more strongly attached to the titanium surfaces after using toluene, which could withstand the ultrahigh vacuum environment of XPS, as compared to the aqueous solutions, which were removed from the titanium surface when exposed to the ultrahigh vacuum environment of XPS.

  16. Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

    PubMed

    Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

    2015-02-21

    The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

  17. Photoelectron energy peaks at Titan: A statistical overview and comparison to Venus and Mars

    NASA Astrophysics Data System (ADS)

    Wellbrock, Anne; Jones, Geraint; Coates, Andrew

    The Cassini CAPS Electron Spectrometer (ELS) has observed discrete energy peaks at 24.1 eV in the electron spectra in Titan's ionosphere. These electrons are believed to be photoelectrons generated due to the ionisation of N2 by the strong solar He II (30.4nm) line. They are generally observed in Titan's dayside ionosphere, because this is where neutral N2 particles can be ionized by solar radiation. Coates et al. (2007) discuss initial observations of these photoelectrons in Titan's distant tail during the Titan encounter 'T9'. Wellbrock et al. (2012) describe three other case studies where these photoelectrons were observed at large distances from Titan. The photoelectrons are unlikely to have originated at these locations because of low neutral N2 densities. The most likely explanation for their existence at these locations is that they travelled along magnetic field lines to the observation sites from the dayside ionosphere, where they were created. Hybrid modelling results support this idea (Wellbrock et al., 2012). In this paper we continue the study of photoelectrons at Titan by performing a statistical overview of photoelectron observation in Titan's ionosphere and exosphere. Similar photoelectron energy peaks are observed at Mars and Venus due to the ionisation of CO2 and O (Frahm et al., 2006, Coates et al., 2008, 2011). We compare the morphology of photoelectron observations at Titan, Mars and Venus and discuss how they can be used to improve our understanding of the complex magnetic environment surrounding unmagnetised bodies with an atmosphere.

  18. Vibrationally resolved anion photoelectron spectroscopy of metal clusters

    NASA Astrophysics Data System (ADS)

    Miller, Stephen R.

    Vibrationally resolved anion photoelectron spectroscopy of metal clusters Vibrationally resolved anion photoelectron spectroscopy (APES) and density functional theory (DFT) are applied to the study of structure and reactivity in small metal containing molecules. The studies described fall into two general categories: the study of bare metal clusters and the study of metal/organic ligand reactions. The current lack of spectroscopic data for small, bare gas-phase metal compounds makes the experimental study of such compounds important for understanding structure and bonding in open-shell metallic species. The heteronuclear diatomic anions MCu- (M = Cr, Mo) were prepared in a flowing afterglow ion-molecule reactor, and studied experimentally with APES. Anion and neutral vibrational frequencies and MCu electron affinities were obtained for both systems. The experiments were supplemented by DFT calculations. The combined use of experiment and theory allows for the assignment of both photoelectron spectra, including a reassignment of the CrCu ground state reported in the literature. Similarly, DFT was used to assign the anionic/neutral electronic states observed in the photoelectron spectra of Al3- and Al3O-. The study of partially ligated organometallic complexes offers a means of examining the interactions between metal atoms and individual ligand molecules. DFT was used to assign electronic states observed in the photoelectron spectra of NbC2H2-, NbC4H4 -NbC6H6- and VC6H 6-. Comparison of the NbnHn - (n = 2, 4, 6) spectra (obtained through the reaction of C2 H4 and Nb) with DFT results provides the first direct spectroscopic evidence of the conversion of ethylene to benzene by a gas phase metal atom. Experiments were used to probe the reactivity of Y with C2H 4 in an effort to examine the generality of the metal induced C 2H4 dehydrogenation/cyclization reactions. Some of the key products in the Y reactions were YC2H-, YC 2H2-, and YC6H5 -. However, the results

  19. Scanning electron and atomic force microscopy, and raman and x-ray photoelectron spectroscopy characterization of near-isogenic soft and hard wheat kernels and corresponding flours

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) are used to investigate vitreous (hard) and non-vitreous (soft) wheat kernels and their corresponding wheat flours. AFM data reveal two different microstructures. The vitreous kernel reveals a granular text...

  20. X-Ray Photoelectron Spectroscopy Study of the Effect of Hydrocarbon Contamination on Poly(Tetrafluoroethylene) Exposed to a Nitrogen Plasma

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1993-01-01

    In this note, we show that X-ray photoelectron Spectroscopy (XPS) data and the changes in surface properties attending exposure of poly(tetrafluoroethylene) (PTFE) films to a nitrogen plasma can likewise be misinterpreted when the interfering role of minor surface hydrocarbon contamination is not taken into account.

  1. X-Ray Photoelectron Spectroscopy Study of the Effect of Hydrocarbon Contamination on Poly(Tetrafluoroethylene) Exposed to a Nitrogen Plasma

    NASA Technical Reports Server (NTRS)

    Golub, Morton A.; Lopata, Eugene S.; Finney, Lorie S.

    1993-01-01

    It has been shown that unless the surface of poly(tetrafluoroethylene)(PTFE) is free of hydrocarbon contamination, anomalous changes in the oxygen and fluorine contents, as measured by X-ray photoelectron spectroscopy (XPS), and hence also the surface properties, may be improperly ascribed to a PTFE film exposed to a oxygen plasma.

  2. Chemical Visualization of a GaN p-n junction by XPS.

    PubMed

    Caliskan, Deniz; Sezen, Hikmet; Ozbay, Ekmel; Suzer, Sefik

    2015-01-01

    We report on an operando XPS investigation of a GaN diode, by recording the Ga2p3/2 peak position under both forward and reverse bias. Areal maps of the peak positions under reverse bias are completely decoupled with respect to doped regions and allow a novel chemical visualization of the p-n junction in a 2-D fashion. Other electrical properties of the device, such as leakage current, resistivity of the domains are also tapped via recording line-scan spectra. Application of a triangular voltage excitation enables probing photoresponse of the device. PMID:26359762

  3. Chemical Visualization of a GaN p-n junction by XPS

    PubMed Central

    Caliskan, Deniz; Sezen, Hikmet; Ozbay, Ekmel; Suzer, Sefik

    2015-01-01

    We report on an operando XPS investigation of a GaN diode, by recording the Ga2p3/2 peak position under both forward and reverse bias. Areal maps of the peak positions under reverse bias are completely decoupled with respect to doped regions and allow a novel chemical visualization of the p-n junction in a 2-D fashion. Other electrical properties of the device, such as leakage current, resistivity of the domains are also tapped via recording line-scan spectra. Application of a triangular voltage excitation enables probing photoresponse of the device. PMID:26359762

  4. In Situ Studies of Surface Mobility on Noble Metal Model Catalysts Using STM and XPS at Ambient Pressure

    SciTech Connect

    Butcher, Derek Robert

    2010-06-01

    High Pressure Scanning Tunneling Microscopy (HP-STM) and Ambient Pressure X-ray Photoelectron Spectroscopy were used to study the structural properties and catalytic behavior of noble metal surfaces at high pressure. HP-STM was used to study the structural rearrangement of the top most atomic surface layer of the metal surfaces in response to changes in gas pressure and reactive conditions. AP-XPS was applied to single crystal and nanoparticle systems to monitor changes in the chemical composition of the surface layer in response to changing gas conditions. STM studies on the Pt(100) crystal face showed the lifting of the Pt(100)-hex surface reconstruction in the presence of CO, H2, and Benzene. The gas adsorption and subsequent charge transfer relieves the surface strain caused by the low coordination number of the (100) surface atoms allowing the formation of a (1 x 1) surface structure commensurate with the bulk terminated crystal structure. The surface phase change causes a transformation of the surface layer from hexagonal packing geometry to a four-fold symmetric surface which is rich in atomic defects. Lifting the hex reconstruction at room temperature resulted in a surface structure decorated with 2-3 nm Pt adatom islands with a high density of step edge sites. Annealing the surface at a modest temperature (150 C) in the presence of a high pressure of CO or H2 increased the surface diffusion of the Pt atoms causing the adatom islands to aggregate reducing the surface concentration of low coordination defect sites. Ethylene hydrogenation was studied on the Pt(100) surface using HP-STM. At low pressure, the lifting of the hex reconstruction was observed in the STM images. Increasing the ethylene pressure to 1 Torr, was found to regenerate the hexagonally symmetric reconstructed phase. At room temperature ethylene undergoes a structural rearrangement to form ethylidyne. Ethylidyne preferentially binds at the three-fold hollow sites, which

  5. Corrosion and degradation studies utilizing X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Hixson, Holly Gwyndolen

    1997-08-01

    This dissertation involves studies of corrosion behavior at the surface of various metal samples, as well as the degradation of wool fibers obtained from the Star-Spangled Banner. Molybdenum metal and iron-zinc alloys were examined under corrosive conditions, and the degradation of the wool fibers was studied. The behavior of a polished molybdenum metal surface upon exposure to both aerated and deaerated water and 1.0 M NaCl solution was studied by X-ray Photoelectron Spectroscopy (XPS). Exposure to deaerated water and NaCl failed to produce oxidation of the metal surfaces, but exposing the polished metal surface to aerated water produced significant oxidation. Metal surfaces cleaned by argon-ion etching were found to be inert to oxidation by aerated water. The etching process also appears to passivate the metal surface. The behavior of molybdenum metal in 0.5 M Hsb2SOsb4 treated at various potentials has been studied using core and valence band XPS. The study indicates that Mosp{IV} and Mosp{VI} (including possibly Mosp{V} in some cases) were formed as the potential of the system was increased within the active range of molybdenum. The corrosive behavior of iron-zinc alloys that have been electroplated on plain steel in both aerated and deaerated quadruply-distilled water has been studied using XPS. Several different iron-zinc alloys were electroplated for comparative purposes: an iron-rich alloy, a zinc-rich alloy, and an alloy of similar iron and zinc composition. Treatment in aerated water produces oxidation for the iron-rich and similar composition alloys, but the oxide is reduced for the zinc-rich alloy. Degradation of the fibers in the original Star-Spangled Banner has been monitored using XPS and Scanning Electron Microscopy (SEM). Comparison of white and red wool fibers and linen fibers from the flag with new, mechanically-abraded, and chemically-treated white, red, and linen fibers, respectively, was performed in an attempt to determine the fibers' levels

  6. Calcination products of gibbsite studied by X-ray diffraction, XPS and solid-state NMR

    SciTech Connect

    Malki, A.; Mekhalif, Z.; Detriche, S.; Fonder, G.; Boumaza, A.; Djelloul, A.

    2014-07-01

    The changes caused by heat treatment of gibbsite powder at 300–1473 K were studied using the X-ray diffraction (XRD), X-ray photoemission (XPS) spectra and {sup 27}Al magic angle spinning nuclear magnetic resonance spectroscopy ({sup 27}Al MAS NMR). XRD analysis indicates that the transformation sequence involves the formation of κ-Al{sub 2}O{sub 3} as an intermediate phase between χ- and α-Al{sub 2}O{sub 3}. The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. XPS analysis indicates that the ratio of aluminium atoms to oxygen atoms in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3} increases, whereas the expected ratio is observed in α-Al{sub 2}O{sub 3}. The percentage of AlO{sub 4} units in the transition aluminas follows the same behaviour as the ratio of Al/O. - Graphical abstract: The percentage of AlO{sub 4} units in transition aluminas follows the same behaviour as the ratio of Al/O. - Highlights: • Calcination products of gibbsite studied by XRD, XPS and solid-state NMR. • The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. • The Al/O atomic ratio determined by XPS is larger than 2/3 in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3}. • The percentage of AlO{sub 4} in the aluminas follows the same behaviour as the Al/O atomic ratio.

  7. Valence and origin of metal-insulator transition in Mn doped SrRuO{sub 3} studied by electrical transport, X-ray photoelectron spectroscopy and LSDA+U calculation

    SciTech Connect

    Sahu, Ranjan K.; Pandey, Sudhir K.; Pathak, L.C.

    2011-03-15

    We have studied the valence and electronic properties of Mn doped SrRuO{sub 3} using electrical transport measurement, X-ray photoelectron spectroscopy (XPS) and local (spin) density approximation plus Coulomb interaction strength calculation (LSDA+U). The resistivity data revealed that the system undergoes transition from metal to insulator at the critical Mn doping level, x{approx}0.2, which is accompanied by the structural transition from orthorhombic to tetragonal crystal symmetry. Besides, the significant reduction of the spectral weight at the coherent zone (0.8 eV) of the valence band is observed for x>0.2. The core XPS spectra suggest that both the transition elements exist in the mixed ionic pair, Ru{sup +4}/Ru{sup +5{r_reversible}}Mn{sup +3}/Mn{sup +4}. The detail analysis of the results suggests that the Coulomb correlation effect in conjugation with localization of the charge carriers predominate over the mixed ionic pair effect and responsible for the metal-insulator transition in the series. -- Graphical Abstract: XPS data and electrical transport data show that doping of Mn in metallic SrRuO{sub 3} induces mixed ionic pair Ru(IV)/Ru(V){r_reversible}Mn(III)/Mn(IV) and the system undergoes a transition from metal to insulator at the critical Mn doping level, x{approx}0.2. The origin for the metal-insulator transition has been discussed. Display Omitted Research highlights: {yields} We have investigated the electronic properties of SrRu{sub 1-x}Mn{sub x}O{sub 3} spectroscopically, which shows metal-insulator transition at the critical Mn doping concentartion x{approx}0.2. {yields} We report the valence states of Ru and Mn in the series. {yields} We also report the responsible mechanism for the metal-insulator transition in the series.

  8. Acid-Base Interactions of Polystyrene Sulfonic Acid in Amorphous Solid Dispersions Using a Combined UV/FTIR/XPS/ssNMR Study.

    PubMed

    Song, Yang; Zemlyanov, Dmitry; Chen, Xin; Nie, Haichen; Su, Ziyang; Fang, Ke; Yang, Xinghao; Smith, Daniel; Byrn, Stephen; Lubach, Joseph W

    2016-02-01

    This study investigates the potential drug-excipient interactions of polystyrene sulfonic acid (PSSA) and two weakly basic anticancer drugs, lapatinib (LB) and gefitinib (GB), in amorphous solid dispersions. Based on the strong acidity of the sulfonic acid functional group, PSSA was hypothesized to exhibit specific intermolecular acid-base interactions with both model basic drugs. Ultraviolet (UV) spectroscopy identified red shifts, which correlated well with the color change observed in lapatinib-PSSA solutions. Fourier transform infrared (FTIR) spectra suggest the protonation of the quinazoline nitrogen atom in both model compounds, which agrees well with data from the crystalline ditosylate salt of lapatinib. X-ray photoelectron spectroscopy (XPS) detected increases in binding energy of the basic nitrogen atoms in both lapatinib and gefitinib, strongly indicating protonation of these nitrogen atoms. (15)N solid-state NMR spectroscopy provided direct spectroscopic evidence for protonation of the quinazoline nitrogen atoms in both LB and GB, as well as the secondary amine nitrogen atom in LB and the tertiary amine nitrogen atom in GB. The observed chemical shifts in the LB-PSSA (15)N spectrum also agree very well with the lapatinib ditosylate salt where proton transfer is known. Additionally, the dissolution and physical stability behaviors of both amorphous solid dispersions were examined. PSSA was found to significantly improve the dissolution of LB and GB and effectively inhibit the crystallization of LB and GB under accelerated storage conditions due to the beneficial strong intermolecular acid-base interaction between the sulfonic acid groups and basic nitrogen centers.

  9. Acid-Base Interactions of Polystyrene Sulfonic Acid in Amorphous Solid Dispersions Using a Combined UV/FTIR/XPS/ssNMR Study.

    PubMed

    Song, Yang; Zemlyanov, Dmitry; Chen, Xin; Nie, Haichen; Su, Ziyang; Fang, Ke; Yang, Xinghao; Smith, Daniel; Byrn, Stephen; Lubach, Joseph W

    2016-02-01

    This study investigates the potential drug-excipient interactions of polystyrene sulfonic acid (PSSA) and two weakly basic anticancer drugs, lapatinib (LB) and gefitinib (GB), in amorphous solid dispersions. Based on the strong acidity of the sulfonic acid functional group, PSSA was hypothesized to exhibit specific intermolecular acid-base interactions with both model basic drugs. Ultraviolet (UV) spectroscopy identified red shifts, which correlated well with the color change observed in lapatinib-PSSA solutions. Fourier transform infrared (FTIR) spectra suggest the protonation of the quinazoline nitrogen atom in both model compounds, which agrees well with data from the crystalline ditosylate salt of lapatinib. X-ray photoelectron spectroscopy (XPS) detected increases in binding energy of the basic nitrogen atoms in both lapatinib and gefitinib, strongly indicating protonation of these nitrogen atoms. (15)N solid-state NMR spectroscopy provided direct spectroscopic evidence for protonation of the quinazoline nitrogen atoms in both LB and GB, as well as the secondary amine nitrogen atom in LB and the tertiary amine nitrogen atom in GB. The observed chemical shifts in the LB-PSSA (15)N spectrum also agree very well with the lapatinib ditosylate salt where proton transfer is known. Additionally, the dissolution and physical stability behaviors of both amorphous solid dispersions were examined. PSSA was found to significantly improve the dissolution of LB and GB and effectively inhibit the crystallization of LB and GB under accelerated storage conditions due to the beneficial strong intermolecular acid-base interaction between the sulfonic acid groups and basic nitrogen centers. PMID:26716395

  10. Femtosecond photoelectron point projection microscope

    SciTech Connect

    Quinonez, Erik; Handali, Jonathan; Barwick, Brett

    2013-10-15

    By utilizing a nanometer ultrafast electron source in a point projection microscope we demonstrate that images of nanoparticles with spatial resolutions of the order of 100 nanometers can be obtained. The duration of the emission process of the photoemitted electrons used to make images is shown to be of the order of 100 fs using an autocorrelation technique. The compact geometry of this photoelectron point projection microscope does not preclude its use as a simple ultrafast electron microscope, and we use simple analytic models to estimate temporal resolutions that can be expected when using it as a pump-probe ultrafast electron microscope. These models show a significant increase in temporal resolution when comparing to ultrafast electron microscopes based on conventional designs. We also model the microscopes spectroscopic abilities to capture ultrafast phenomena such as the photon induced near field effect.

  11. Consequences of electron correlation for XPS binding energies: Representative case for C(1s) and O(1s) XPS of CO

    NASA Astrophysics Data System (ADS)

    Bagus, Paul S.; Sousa, Carme; Illas, Francesc

    2016-10-01

    In this paper, we present a study of the signs and the magnitudes of the errors of theoretical binding energies, BE's, of the C(1s) and O(1s) core-levels compared to BE's measured in X-Ray photoemission, XPS, experiments. In particular, we explain the unexpected sign of the error of the Hartree-Fock C(1s) BE, which is larger than experiment, in terms of correlation effects due to the near degeneracy of the CO(1π) and CO(2π) levels and show how taking this correlation into account leads to rather accurate predicted BE's. We separate the initial state contributions of this near degeneracy, present for the ground state wavefunction, from the final state near degeneracy effects, present for the hole state wavefunctions. Thus, we are able to establish the importance for the core-level BE's of initial state charge redistribution due to the π near-degeneracy. While the results for CO are interesting in their own right, we also consider whether our conclusions for CO are relevant for the analysis of XPS spectra of a wider range of molecules.

  12. Drying methods for XPS analysis of PureVision™, Focus ® Night&Day™ and conventional hydrogel contact lenses

    NASA Astrophysics Data System (ADS)

    Karlgard, Caroline C. S.; Sarkar, Dilip K.; Jones, Lyndon W.; Moresoli, Christine; Leung, K. T.

    2004-05-01

    The surface composition of hydrogel contact lenses that contain silicon-based monomers, PureVision™ (balafilcon A) and Focus ® Night&Day™ (lotrafilcon A), were investigated by X-ray photoelectron spectroscopy (XPS). Conventional and daily disposable hydrogel lenses based on hydroxyethyl methacrylate (HEMA) were also studied, with the commonly prescribed 1-day Acuvue ® lens (etafilcon A) used as a control. All the lenses were pre-washed and dehydrated by three different methods, including drying in air, drying in nitrogen or freezing with subsequent freeze-drying, before the XPS analysis. The lenses dried in air had more impurities on the surface, and the lenses that were freeze-dried lost transparency, suggesting that drying lenses in nitrogen is the preferred preparation method for XPS analysis. Surface compositions for all lens materials were obtained and this data can be used as a control/base-value for future analysis of the interactions of soft contact lens materials with chemicals such as drugs or tear components.

  13. X-ray photoelectron spectroscopy study of disordering in Gd2(Ti1-xZrx)2O7 pyrochlores.

    PubMed

    Chen, J; Lian, J; Wang, L M; Ewing, R C; Wang, R G; Pan, W

    2002-03-11

    The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25 < x < or =0.75), the corresponding O 1s XPS spectrum merges into a single symmetric peak. This confirms that the cation antisite disorder occurs simultaneously with anion disorder. Furthermore, the O 1s XPS spectrum of Gd2Zr2O7 experimentally suggests the formation of a split vacancy.

  14. X-ray Photoelectron Spectroscopy Study of Disordering in Gd2(Ti1-xZrx)2O7 Pyrochlores

    NASA Astrophysics Data System (ADS)

    Chen, J.; Lian, J.; Wang, L. M.; Ewing, R. C.; Wang, R. G.; Pan, W.

    2002-03-01

    The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25XPS spectrum merges into a single symmetric peak. This confirms that the cation antisite disorder occurs simultaneously with anion disorder. Furthermore, the O 1s XPS spectrum of Gd2Zr2O7 experimentally suggests the formation of a split vacancy.

  15. Mixed adlayer of alkanethiol and peptide on GaAs(100): quantitative characterization by X-ray photoelectron spectroscopy.

    PubMed

    Wampler, Heeyeon P; Zemlyanov, Dmitry Y; Lee, Kangho; Janes, David B; Ivanisevic, Albena

    2008-04-01

    Homogeneous and mixed adlayers composed of an alkanethiol (1-octadecanethiol, ODT) and a peptide (CGISYGRKKRRQRRR) on GaAs(100) were formed in two different solvent systems: phosphate-buffered saline (PBS) and N,N-dimethylformamide (DMF). The chemical composition of each adlayer was characterized by X-ray photoelectron spectroscopy (XPS). The data showed that the makeup of the adlayer and its stability largely depends on the solvent used. Angle-resolved XPS also revealed that the adlayer thickness and tilt angles were different from values obtained from ellipsometry measurements and vastly varied between the two solvents used. The coverage data extracted from the XPS measurements indicated that homogeneous adlayers of peptide in PBS buffer form a multilayered film. Homogeneous alkanethiol adlayers exhibited monolayer coverage under all solvent treatments. Coadsorbed layers containing both alkanethiol and peptide have fractional monolayer coverage in both solvents. PMID:18275237

  16. Gold deposition on pyrite and the common sulfide minerals: An STM/STS and SR-XPS study of surface reactions and Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Mikhlin, Yuri L.; Romanchenko, Alexander S.

    2007-12-01

    Gold species spontaneously deposited on pyrite and chalcopyrite, pyrrhotite, galena, sphalerite from HAuCl 4 solutions at room temperature, as well as the state of the reacted mineral surfaces have been characterized using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), scanning tunneling microscopy and tunneling spectroscopy (STM/STS). The deposition of silver from 10 -4 M AgNO 3 has been examined for comparison. Gold precipitates as metallic nanoparticles (NPs) from about 3 nm to 30 nm in diameter, which tends to aggregate forming larger particles, especially on pyrite. The Au 4f binding energies increase up to 1 eV with decreasing size of individual Au 0 NPs, probably due to the temporal charging in the final state. Concurrently, a positive correlation between the tunneling current and the particle size was found in STS. Both these size effects were observed for unusually large, up to 20 nm Au particles. In contrast, silver deposited on the minerals as nanoparticles of semiconducting sulfide showed no shifts of photoelectron lines and different tunneling spectra. The quantity of gold deposited on pyrite and other minerals increased with time; it was lower for fracture surfaces and it grew if minerals were moderately pre-oxidized, while the preliminary leaching in Fe(III)-bearing media inhibited the following Au deposition. After the contact of polished minerals with 10 -4 M AuCl4- solution (pH 1.5) for 10 min, the gold uptake changed in the order CuFeS 2 > ZnS > PbS > FeAsS > FeS 2 > Fe 7S 8. It was noticed that the open circuit (mixed) potentials of the minerals varied in approximately the same order, excepting chalcopyrite. We concluded that the potentials of minerals were largely determined by Fe(II)/Fe(III) couple, whereas the reduction of gold complexes had a minor effect. As a result, the deposition of gold, although it proceeded via the electrochemical mechanism, increased with decreasing potential. This suggests, in particular, that the

  17. In situ x-ray photoelectron spectroscopy for electrochemical reactions in ordinary solvents

    SciTech Connect

    Masuda, Takuya; Yoshikawa, Hideki; Kobata, Masaaki; Kobayashi, Keisuke; Noguchi, Hidenori; Kawasaki, Tadahiro; Uosaki, Kohei

    2013-09-09

    In situ electrochemical X-ray photoelectron spectroscopy (XPS) apparatus, which allows XPS at solid/liquid interfaces under potential control, was constructed utilizing a microcell with an ultra-thin Si membrane, which separates vacuum and a solution. Hard X-rays from a synchrotron source penetrate into the Si membrane surface exposed to the solution. Electrons emitted at the Si/solution interface can pass through the membrane and be analyzed by an analyzer placed in vacuum. Its operation was demonstrated for potential-induced Si oxide growth in water. Effect of potential and time on the thickness of Si and Si oxide layers was quantitatively determined at sub-nanometer resolution.

  18. X-ray photoelectron spectroscopic analysis of rice kernels and flours: Measurement of surface chemical composition.

    PubMed

    Nawaz, Malik A; Gaiani, Claire; Fukai, Shu; Bhandari, Bhesh

    2016-12-01

    The objectives of this study were to evaluate the ability of X-ray photoelectron spectroscopy (XPS) to differentiate rice macromolecules and to calculate the surface composition of rice kernels and flours. The uncooked kernels and flours surface composition of the two selected rice varieties, Thadokkham-11 (TDK11) and Doongara (DG) demonstrated an over-expression of lipids and proteins and an under-expression of starch compared to the bulk composition. The results of the study showed that XPS was able to differentiate rice polysaccharides (mainly starch), proteins and lipids in uncooked rice kernels and flours. Nevertheless, it was unable to distinguish components in cooked rice samples possibly due to complex interactions between gelatinized starch, denatured proteins and lipids. High resolution imaging methods (Scanning Electron Microscopy and Confocal Laser Scanning Microscopy) were employed to obtain complementary information about the properties and location of starch, proteins and lipids in rice kernels and flours. PMID:27374542

  19. Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules.

    PubMed

    Boll, Rebecca; Rouzée, Arnaud; Adolph, Marcus; Anielski, Denis; Aquila, Andrew; Bari, Sadia; Bomme, Cédric; Bostedt, Christoph; Bozek, John D; Chapman, Henry N; Christensen, Lauge; Coffee, Ryan; Coppola, Niccola; De, Sankar; Decleva, Piero; Epp, Sascha W; Erk, Benjamin; Filsinger, Frank; Foucar, Lutz; Gorkhover, Tais; Gumprecht, Lars; Hömke, André; Holmegaard, Lotte; Johnsson, Per; Kienitz, Jens S; Kierspel, Thomas; Krasniqi, Faton; Kühnel, Kai-Uwe; Maurer, Jochen; Messerschmidt, Marc; Moshammer, Robert; Müller, Nele L M; Rudek, Benedikt; Savelyev, Evgeny; Schlichting, Ilme; Schmidt, Carlo; Scholz, Frank; Schorb, Sebastian; Schulz, Joachim; Seltmann, Jörn; Stener, Mauro; Stern, Stephan; Techert, Simone; Thøgersen, Jan; Trippel, Sebastian; Viefhaus, Jens; Vrakking, Marc; Stapelfeldt, Henrik; Küpper, Jochen; Ullrich, Joachim; Rudenko, Artem; Rolles, Daniel

    2014-01-01

    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C(8)H(5)F) and dissociating, laser-aligned 1,4-dibromobenzene (C(6)H(4)Br(2)) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

  20. Composition of RF-sputtered refractory compounds determined by X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.; Brainard, W. A.

    1978-01-01

    RF-sputtered coatings of CrB2, MoSi2, Mo2C, TiC, and MoS2 were examined by X-ray photoelectron spectroscopy (XPS). Data on stoichiometry, impurity content, and chemical bonding were obtained. The influences of sputtering target history, deposition time, RF power level, and substrate bias were studied. Significant deviations from stoichiometry and high oxide levels were related to target outgassing. The effect of substrate bias depended on the particular coating material studied.

  1. Satellite structure in the Argon 1s photoelectron spectrum

    SciTech Connect

    Azuma, Y.; LeBrun, T.; MacDonald, M.; Southworth, S.H.

    1995-08-01

    Atomic inner-shell photoelectron spectra typically display several relatively weak {open_quotes}satellite peaks{close_quotes} at higher ionization energy than the primary peak. Such satellite peaks are associated with final-state configurations corresponding to ionization of an inner-shell electron and excitation or ionization of one or more valence electrons. The observation of satellite peaks demonstrates that the independent-electron picture is inadequate to describe atomic structure and the photoionization process. The measured energies and intensities of photoelectron satellites provide sensitive tests of many-electron theoretical models. We recorded the Ar 1s photoelectron spectrum on beam line X-24A at an X-ray energy of 3628 eV. The primary peak at 3206 eV ionization energy was recorded at an observed resolution of 1.8 eV (FWHM). The satellite structure shows remarkable similarity to that recorded in the suprathreshold region of the Ar K photoabsorption cross section, demonstrating the manner in which these techniques complement each other. Surprisingly, while the region just above the K threshold in Ar was the subject of several theoretical studies using multi-configuration calculations, we find good agreement between our results and those of Dyall and collaborators using a shake model.

  2. A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions.

    PubMed

    Brown, Matthew A; Redondo, Amaia Beloqui; Jordan, Inga; Duyckaerts, Nicolas; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Müächler, Jean-Pierre; Birrer, Mario; Honegger, Juri; Wetter, Reto; Wörner, Hans Jakob; van Bokhoven, Jeroen A

    2013-07-01

    A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented. PMID:23902081

  3. A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions

    SciTech Connect

    Brown, Matthew A.; Redondo, Amaia Beloqui; Duyckaerts, Nicolas; Mächler, Jean-Pierre; Jordan, Inga; Wörner, Hans Jakob; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Birrer, Mario; Honegger, Juri; Wetter, Reto; Bokhoven, Jeroen A. van

    2013-07-15

    A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.

  4. Investigations on surface chemical analysis using X-ray photoelectron spectroscopy and optical properties of Dy3+-doped LiNa3P2O7 phosphor

    NASA Astrophysics Data System (ADS)

    Munirathnam, K.; Dillip, G. R.; Chaurasia, Shivanand; Joo, S. W.; Deva Prasad Raju, B.; John Sushma, N.

    2016-08-01

    Near white-light emitting LiNa3P2O7:Dy3+ phosphors were prepared by a conventional solid-state reaction method. The orthorhombic crystal structure of the phosphors was confirmed using X-ray diffraction (XRD), and the valence states of the surface elements were determined from the binding energies of Li 1s, O 1s, Na 1s, P 2p, and Dy 3d by X-ray photoelectron spectroscopy (XPS). Attenuated total reflectance (ATR) - Fourier transform infrared (FT-IR) spectroscopy was employed to identify the pyrophosphate groups in the phosphors. Diffuse reflectance spectra (DRS) show the absorption bands of the Dy3+ ions in the host material. Intense blue (481 nm) and yellow (575 nm) emissions were obtained at an excitation wavelength of 351 nm and are attributed to the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ ions, respectively. The combination of these two intense bands generates light emission in the near-white region of the chromaticity diagram.

  5. Auger and X-ray PhotoelectronSpectroscopy Study of the Density ofOxygen States in Bismuth, Aluminum, Silicon, and Uranium Oxides

    SciTech Connect

    Teterin, Yu A.; Ivanov, K.E.; Teterin, A. Yu; Lebedev, A.M.; Utkin, I.O.; Vukchevich, L.

    1998-08-03

    The correlation of relative partial electron density at the oxygen ions with the intensity of Auger O KLL lines in Bi2O3, Al2O3, SiO2 and UO2 has been determined by Auger and X-ray photoelectron spectroscopic methods. The dependence of the relative intensities of Auger O KL2-3L2-3 and O KL1L2-3-lines was characterized from the binding energy of O 1s electrons. The electron density of the outer valence levels of oxygen increases as the relative intensities of Anger OKL2-3L2-3 and O KL1L2-3-lines increase. The fine structure observed in the O KL1L2-3 Auger and the O 2s XPS spectra has been explained by the formation of inner valence molecular orbitals (IVMO) from the interaction of electrons of the O 2s and filled metal ns shells.

  6. In situ XPS and MS study of methanol decomposition and oxidation on Pd(111) under millibar pressure range

    NASA Astrophysics Data System (ADS)

    Kaichev, V. V.; Miller, A. V.; Prosvirin, I. P.; Bukhtiyarov, V. I.

    2012-02-01

    The methanol decomposition and oxidation on a Pd(111) single crystal have been investigated in situ using ambient-pressure X-ray photoelectron spectroscopy (XPS) and mass-spectrometry (MS) in the temperature range of 300-600 K. It was found that even in the oxygen presence the methanol decomposition on palladium proceeds through two competitive routes: fast dehydrogenation to CO and H2, and slow decomposition of methanol via the C-O bond scission. The rate of the second route is significant even in the millibar pressure range, which leads to a blocking of the palladium surface by carbon and to a prevention of the further methanol conversion. As a result, no gas phase products of methanol decomposition were detected by mass-spectrometry at 0.1 mbar CH3OH in the whole temperature range. The methanol C-O bond scission produces CHx species, which fast dehydrogenate to atomic carbon even at room temperature and further partially dissolve in the palladium bulk at 400 K with the formation of the PdCx phase. According to in situ XPS data, the PdCx phase forms even in the oxygen excess. The application of an in situ XPS-MS technique unambiguously shows a good correlation between a decrease in the surface concentration of all carbon-containing species and the rate of methanol conversion. Since these carbon species have a high reactivity towards oxygen, heating of Pd(111) above 450 K in a methanol-oxygen mixture yields CO, CO2, and water. The product distribution indicates that the main route of methanol conversion is the dehydrogenation of methanol to CO and hydrogen. However, under the experimental conditions used, hydrogen is completely oxidized to water, while CO is partially oxidized to CO2. No palladium oxide was detected by XPS in these conditions.

  7. Zero kinetic energy photoelectron spectroscopy of triphenylene

    SciTech Connect

    Harthcock, Colin; Zhang, Jie; Kong, Wei

    2014-06-28

    We report vibrational information of both the first electronically excited state and the ground cationic state of jet-cooled triphenylene via the techniques of resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The first excited electronic state S{sub 1} of the neutral molecule is of A{sub 1}′ symmetry and is therefore electric dipole forbidden in the D{sub 3h} group. Consequently, there are no observable Franck-Condon allowed totally symmetric a{sub 1}′ vibrational bands in the REMPI spectrum. All observed vibrational transitions are due to Herzberg-Teller vibronic coupling to the E′ third electronically excited state S{sub 3}. The assignment of all vibrational bands as e′ symmetry is based on comparisons with calculations using the time dependent density functional theory and spectroscopic simulations. When an electron is eliminated, the molecular frame undergoes Jahn-Teller distortion, lowering the point group to C{sub 2v} and resulting in two nearly degenerate electronic states of A{sub 2} and B{sub 1} symmetry. Here we follow a crude treatment by assuming that all e′ vibrational modes resolve into b{sub 2} and a{sub 1} modes in the C{sub 2v} molecular frame. Some observed ZEKE transitions are tentatively assigned, and the adiabatic ionization threshold is determined to be 63 365 ± 7 cm{sup −1}. The observed ZEKE spectra contain a consistent pattern, with a cluster of transitions centered near the same vibrational level of the cation as that of the intermediate state, roughly consistent with the propensity rule. However, complete assignment of the detailed vibrational structure due to Jahn-Teller coupling requires much more extensive calculations, which will be performed in the future.

  8. Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

    PubMed

    Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

    2015-09-21

    A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

  9. Investigations on the low voltage cathodoluminescence stability and surface chemical behaviour using Auger and X-ray photoelectron spectroscopy on LiSrBO{sub 3}:Sm{sup 3+} phosphor

    SciTech Connect

    Pitale, Shreyas S.; Nagpure, I.M.; Kumar, Vinay; Ntwaeaborwa, O.M.; Terblans, J.J.; Swart, H.C.

    2011-07-15

    Highlights: {yields} Stable orange-red cathodoluminescence observed from LiSrBO{sub 3}:Sm{sup 3+} phosphor. {yields} In situ Auger electron spectroscopy, while monitoring the CL output reduction, reveals surface concentration modification of Li, Sr, B and O atoms. {yields} X-ray photoelectron spectroscopy confirms the formation of SrO{sub 2} layer due to the electron stimulated surface chemical reactions (ESSCRs). This layer is possibly contributing to the surface chemical stability and prevents further degradation. -- Abstract: Orange-red emissive LiSrBO{sub 3}:Sm{sup 3+} phosphors were synthesized through the solid-state reaction method. Under UV radiation (221 nm) and low-voltage electron beam (2 keV, 12 mA/cm{sup 2}) excitation, the Sm{sup 3+} doped LiSrBO{sub 3} phosphor shows emission corresponding to the characteristic {sup 4}G{sub 5/2}-{sup 6}H{sub 7/2} transitions of Sm{sup 3+} with the strongest emission at 601 nm. A high stability of cathodoluminescence (CL) emission during prolong electron bombardment with low-energy electrons was observed. Surface sensitive diagnostic tools such as Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to study the surface chemistry. AES results revealed modifications in the surface concentrations of Li, Sr, B, O and C on the surface of the LiSrBO{sub 3}:Sm{sup 3+} phosphor as indicated by the changes in their Auger peak to peak heights (APPH) as a function of electron dose. Observed changes in the high resolution XPS spectra of the LiSrBO{sub 3}:Sm{sup 3+} surface irradiated with the low energy electron beam provide evidence of compositional and structural changes as a result of the electron beam stimulated surface chemical reactions (ESSCRs). Additional SrO{sub 2} was identified by XPS on the phosphor surface after it received an electron dose of 300 C/cm{sup 2} together with the increase in the concentrations of chemical species containing the B-C-O bonding. The new surface chemical

  10. High resolution photoelectron spectroscopy of clusters of Group V elements

    SciTech Connect

    Wang, Lai-sheng; Niu, B.; Lee, Y.T.; Shirley, D.A.

    1989-07-01

    High resolution HeI (580{angstrom}) photoelectron spectra of As{sub 2}, As{sub 4}, and P{sub 4} were obtained with a newly-built high temperature molecular beam source. Vibrational structure was resolved in the photoelectron spectra of the three cluster species. The Jahn-Teller effect is discussed for the {sup 2}E and {sup 2}T{sub 2} states of P{sub 4}{sup +} and As{sub 4}{sup +}. As a result of the Jahn-Teller effect, the {sup 2}E state splits into two bands, and the {sup 2}T{sub 2} state splits into three bands, in combination with the spin-orbit effect. It was observed that the {nu}{sub 2} normal vibrational mode was involved in the vibronic interaction of the {sup 2}E state, while both the {nu}{sub 2} and {nu}{sub 3} modes were active in the {sup 2}T{sub 2} state. 26 refs., 5 figs., 3 tabs.

  11. In-situ X-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

    SciTech Connect

    Salmeron, Miquel; Yamamoto, S.; Bluhm, H.; Andersson, K.; Ketteler, G.; Ogasawara, H.; Salmeron, M.; Nilsson, A.

    2007-10-29

    X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing the elemental composition of surfaces and the local chemical environment of adsorbed species. Conventional XPS experiments have been limited to ultrahigh vacuum (UHV) conditions due to a short mean free path of electrons in a gas phase. The recent advances in instrumentation coupled with third-generation synchrotron radiation sources enables in-situ XPS measurements at pressures above 5 Torr. In this review, we describe the basic design of the ambient pressure XPS setup that combines differential pumping with an electrostatic focusing. We present examples of the application of in-situ XPS to studies of water adsorption on the surface of metals and oxides including Cu(110), Cu(111), TiO2(110) under environmental conditions of water vapor pressure. On all these surfaces we observe a general trend where hydroxyl groups form first, followed by molecular water adsorption. The importance of surface OH groups and their hydrogen bonding to water molecules in water adsorption on surfaces is discussed in detail.

  12. Quantitative determination of the oxidation state of iron in biotite using x-ray photoelectron spectroscopy: II. In situ analyses

    SciTech Connect

    Raeburn, S.P. |; Ilton, E.S.; Veblen, D.R.

    1997-11-01

    X-ray photoelectron spectroscopy (XPS) was used to determine Fe(III)/{Sigma}Fe in individual biotite crystals in thin sections of ten metapelites and one syenite. The in situ XPS analyses of Fe(III)/{Sigma}Fe in biotite crystals in the metapelites were compared with published Fe(III)/{Sigma}Fe values determined by Moessbauer spectroscopy (MS) for mineral separates from the same hand samples. The difference between Fe(III)/{Sigma}Fe by the two techniques was greatest for samples with the lowest Fe(III)/{Sigma}Fe (by MS). For eight metamorphic biotites with Fe(III)/{Sigma}Fe = 9-27% comparison of the two techniques yielded a linear correlation of r = 0.94 and a statistically acceptable fit of [Fe(III)/{Sigma}Fe]{sub xps} = [Fe(III)/{Sigma}Fe]{sub ms}. The difference between Fe(III)/{Sigma}Fe by the two techniques was greater for two samples with Fe(III)/{Sigma}Fe {le} 6% (by MS). For biotite in the syenite sample, Fe(III)/{Sigma}Fe determined by both in situ XPS and bulk wet chemistry/electron probe microanalysis were similar. This contribution demonstrates that XPS can be used to analyze bulk Fe(III)/{Sigma}Fe in minerals in thin sections when appropriate precautions taken to avoid oxidation of the near-surface during preparation of samples. 25 refs., 3 figs., 4 tabs.

  13. Experimental Investigations of the Lunar Photoelectron Sheath

    NASA Astrophysics Data System (ADS)

    Dove, A.; Sternovsky, Z.; Wang, X.; Robertson, S. H.; Lapanse, C.; Horanyi, M.; Collette, A.

    2010-12-01

    Solar ultraviolet radiation incident upon the dayside lunar surface produces a photoelectron gas that dominates the near-surface plasma environment, with a typical density of 60 cm-3 and a characteristic scale-length of ~1 m. It has traditionally been difficult to produce a photoelectron gas with sufficient density in a laboratory settings to study its properties. In our initial experiments, the characterization of the photoelectron density above a Zr surface (work function W=4.4 eV) illuminated by Xe excimer lamps (peak emission at a wavelength of 172 nm) indicated that a sheath with a Debye length on the order of 10 cm formed. We characterize the photoelectron population above the surface by utilizing an emissive probe to map the electric potential distribution above the surface, and a Langmuir probe to determine the number density and temperature of the photoelectrons. A grid is placed 7.5 cm above the Zr surface to repel photoelectrons emitted from the chamber walls. Emissive probe measurements show a potential dip of about 2 V extending ~1 cm above the zirconium surface. The size of this potential well is dependent on the number of lamps illuminating the surface, as the density of photoelectrons above the surface increases with greater illumination. The electrons in the sheath have a Maxwellian distribution with an electron temperature around 1 eV (maximum energies are expected to be approximately 2.8 eV). We will use this experimental apparatus to characterize the photoelectron sheath above other surfaces; powders, such as CeO2 have similar work functions, but different photoelectric yields. Lunar soil simulants are expected to have approximately an order of magnitude smaller yield than metallic surfaces, which will act to increase the characteristic length of the photoelectron sheath above the surface. The experiments and accompanying computer simulations are used to guide the development of new instrument concepts for future in situ plasma measurements on

  14. Photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O-

    NASA Astrophysics Data System (ADS)

    Oliveira, Allan M.; Lehman, Julia H.; McCoy, Anne B.; Lineberger, W. Carl

    2016-09-01

    We report the negative ion photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O-. The photoelectron spectra show that 3.49 eV photodetachment produces two distinct electronic states of the neutral hydroxymethoxy radical (H2C(OH)Oṡ). The H2C(OH)Oṡ ground state (X ˜ 2A) photoelectron spectrum exhibits a vibrational progression consisting primarily of the OCO symmetric and asymmetric stretches, the OCO bend, as well as combination bands involving these modes with other, lower frequency modes. A high-resolution photoelectron spectrum aids in the assignment of several vibrational frequencies of the neutral H2C(OH)Oṡ radical, including an experimental determination of the H2C(OH)Oṡ 2ν12 overtone of the H-OCO torsional vibration as 220(10) cm-1. The electron affinity of H2C(OH)Oṡ is determined to be 2.220(2) eV. The low-lying A ˜ 2A excited state is also observed, with a spectrum that peaks ˜0.8 eV above the X ˜ 2A state origin. The A ˜ 2A state photoelectron spectrum is a broad, partially resolved band. Quantum chemical calculations and photoelectron simulations aid in the interpretation of the photoelectron spectra. In addition, the gas phase acidity of methanediol is calculated to be 366(2) kcal mol-1, which results in an OH bond dissociation energy, D0(H2C(OH)O-H), of 104(2) kcal mol-1, using the experimentally determined electron affinity of the hydroxymethoxy radical.

  15. Complementary low energy ion scattering and X-ray photoelectron spectroscopy characterization of polystyrene submitted to N 2/H 2 glow discharge

    NASA Astrophysics Data System (ADS)

    Bonatto, F.; Rovani, S.; Kaufmann, I. R.; Soares, G. V.; Baumvol, I. J. R.; Krug, C.

    2012-02-01

    Low energy ion scattering (LEIS) and X-ray photoelectron spectroscopy (XPS) were used to access the elemental composition and chemical bonding characteristics of polystyrene (PS) surfaces sequentially treated by corona and glow discharge (plasma) processing in N 2/H 2 ambient. The latter has shown activity as suppressor of pathogenic Staphylococcus epidermidis biofilms. LEIS indicated that oxygen from the corona discharge process is progressively replaced by nitrogen at the PS surface. XPS shows C dbnd N and N sbnd C dbnd O chemical groups as significant inhibitors of bacterial adhesion, suggesting application in medical devices.

  16. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments

    SciTech Connect

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo E-mail: xfzheng@mail.ahnu.edu.cn; Zheng, Xianfeng E-mail: xfzheng@mail.ahnu.edu.cn; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2015-06-15

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ∼1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 6{sup 1} and 6{sup 1}1{sup 1} vibronic levels in the S{sub 1} state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1′) REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62 271 ± 3 cm{sup −1}). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique.

  17. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments.

    PubMed

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo; Zheng, Xianfeng; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2015-06-01

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ∼1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 6(1) and 6(1)1(1) vibronic levels in the S1 state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1') REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62,271 ± 3 cm(-1)). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique. PMID:26133827

  18. The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments

    NASA Astrophysics Data System (ADS)

    Qu, Zehua; Li, Chunsheng; Qin, Zhengbo; Zheng, Xianfeng; Yao, Guanxin; Zhang, Xianyi; Cui, Zhifeng

    2015-06-01

    Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ˜1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 61 and 6111 vibronic levels in the S1 state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1') REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62 271 ± 3 cm-1). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique.

  19. X-ray and photoelectron spectroscopy of the structure, reactivity, and electronic structure of semiconductor nanocrystals

    SciTech Connect

    Hamad, K.S.

    2000-05-01

    Semiconductor nanocrystals are a system which has been the focus of interest due to their size dependent properties and their possible use in technological applications. Many chemical and physical properties vary systematically with the size of the nanocrystal and thus their study enables the investigation of scaling laws. Due to the increasing surface to volume ratio as size is decreased, the surfaces of nanocrystals are expected to have a large influence on their electronic, thermodynamic, and chemical behavior. In spite of their importance, nanocrystal surfaces are still relatively uncharacterized in terms of their structure, electronic properties, bonding, and reactivity. Investigation of nanocrystal surfaces is currently limited by what techniques to use, and which methods are suitable for nanocrystals is still being determined. This work presents experiments using x-ray and electronic spectroscopies to explore the structure, reactivity, and electronic properties of semiconductor (CdSe, InAs) nanocrystals and how they vary with size. Specifically, x-ray absorption near edge spectroscopy (XANES) in conjunction with multiple scattering simulations affords information about the structural disorder present at the surface of the nanocrystal. X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) probe the electronic structure in terms of hole screening, and also give information about band lineups when the nanocrystal is placed in electric contact with a substrate. XPS of the core levels of the nanocrystal as a function of photo-oxidation time yields kinetic data on the oxidation reaction occurring at the surface of the nanocrystal.

  20. Near threshold studies of photoelectron satellites

    SciTech Connect

    Heimann, P.A.

    1986-11-01

    Photoelectron spectroscopy and synchrotron radiation have been used to study correlation effects in the rare gases: He, Ne, Ar, Kr, and Xe. Two kinds of time-of-flight electron analyzers were employed to examine photoionization very close to threshold and at higher kinetic energies. Partial cross sections and angular distributions have been measured for a number of photoelectron satellites. The shake-off probability has been determined at some inner-shell resonances. 121 refs., 28 figs., 13 tabs.

  1. XPS and ToF-SIMS analysis of natural rubies and sapphires heat-treated in a reducing (5 mol% H 2/Ar) atmosphere

    NASA Astrophysics Data System (ADS)

    Achiwawanich, S.; James, B. D.; Liesegang, J.

    2008-12-01

    Surface effects on Mong Hsu rubies and Kanchanaburi sapphires after heat treatment in a controlled reducing atmosphere (5 mol% H 2/Ar) have been investigated using advanced surface science techniques including X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Visual appearance of the gemstones is clearly affected by the heat treatment in a reducing atmosphere. Kanchanaburi sapphires, in particular, exhibit Fe-containing precipitates after the heat treatment which have not been observed in previous studies under an inert atmosphere. Significant correlation between changes in visual appearance of the gemstones and variations in surface concentration of trace elements, especially Ti and Fe are observed. The XPS and ToF-SIMS results suggest that; (1) a reducing atmosphere affects the oxidation state of Fe; (2) dissociation of Fe-Ti interaction may occur during heat treatment.

  2. Energetic photoelectrons and the polar rain

    NASA Technical Reports Server (NTRS)

    Decker, Dwight T.; Jasperse, J. R.; Winningham, J. D.

    1990-01-01

    In the daytime midlatitudes, the Low Altitude Plasma Instrument (LAPI) on board the Dynamics Explorer 2 satellite has observed photoelectrons with energies as high as 850 eV. These energetic photoelectrons are an extension of the 'classical' photoelectrons (less than 60 eV) and result from photoionization of neutrals by soft solar X-rays. Since these photoelectrons are produced wherever the solar flux is incident on the earth's atmosphere, they should be present in sunlit polar cap. But in the polar cap, over these same energies, there is a well-known electron population: the polar rain, a low intensity electron flux of magnetospheric origin. Thus, in the sunlit polar cap, an energetic population of electrons should consist of both an ionospheric (photoelectron) and a magnetospheric (polar rain) component. Using numerical solutions of an electron transport equation with appropriate boundary conditions and sunlit polar cap LAPI data, it is shown that the two populations (photoelectron and polar rain) are indeed present and are both needed to explain polar cap observations.

  3. Structural Investigation of Mixed Nitrided Galloaluminophosphates ``AlGaPON'' by EELS, XAS, and XPS Spectroscopies

    NASA Astrophysics Data System (ADS)

    Delsarte, S.; Serin, V.; Flank, A.-M.; Villain, F.; Grange, P.

    2002-01-01

    Amorphous nitrided galloaluminophosphates "AlGaPON" catalysts with nitrogen contents varying from 0 to 23.3 wt% N were obtained by nitriding an Al0.5Ga0.5PO4 precursor under ammonia flow at 750°C in a tubular furnace. The structural changes induced by this treatment were investigated by electron energy loss spectroscopy (EELS), X-ray absorption spectroscopy (XAS), and X-ray photoelecton spectroscopy (XPS). XANES and XPS results indicate that the first-coordination spheres of P, Ga, and Al atoms are modified by nitridation. In particular, the comparison of the P XANES spectra recorded on "AlGaPON" and on a PON phosphorus oxynitride (reference of mixed PO2N2 tetrahedra) reveals that mainly PO2N2 tetrahedra are present in highly nitrided samples. Moreover, the replacement of oxygen by nitrogen probably concerned P-O-Ga bonds rather than P-O-Al. EELS investigation reveals that the precursor is homogeneous at the used probe scale, but indicates that nitridation is accompanied by a loss of homogeneity of the material.

  4. Modeling the PbI2 formation in perovskite solar cells using XRD/XPS patterns

    NASA Astrophysics Data System (ADS)

    Sohrabpoor, Hamed; Elyasi, Majid; Aldosari, Marouf; Gorji, Nima E.

    2016-09-01

    The impact of prolonged irradiation and air humidity on the stability of perovskite solar cells is modeled using X-ray diffraction and X-ray photoelectron spectroscopy patterns reported in the literature. Light or air-moisture causes the formation of a thin PbI2 or oxide defective layers (in nanoscale) at the interface of perovskite/hole-transport-layer or at the junction with metallic back contact. This thin layer blocks the carrier transport/passivation at the interfaces and cause degradation of device parameters. Variation in thickness of defective layers, changes the XRD and XPS peaks. This allows detection and estimation of the type, crystallinity and thickness of the defective layer. A simple model is developed here to extract the thickness of such thin defective layers formed in nanometer scale at the back region of several perovskite devices. Based on this information, corrected energy band diagram of every device before and after degradation/aging is drawn and discussed in order to obtain insight into the carrier transport and charge collection at the barrier region. In addition, graphene contacted perovskite devices are investigated showing that honey-comb network of graphene contact reduces the effect of aging leading to formation of a thinner defective layer at the perovskite surface compared to perovskite devices with conventional inorganic contacts i.e. Au, Al.

  5. XPS characterization of (copper-based) coloured stains formed on limestone surfaces of outdoor Roman monuments

    PubMed Central

    2012-01-01

    Limestone basements holding bronzes or other copper alloys artefacts such as sculptures, decorations and dedicatory inscriptions are frequently met both in modern and ancient monuments. In outdoor conditions, such a combination implies the corrosion products of the copper based alloy, directly exposed to rainwater, will be drained off and migrate through the porous surfaces, forming stains of different colours and intensities, finally causing the limestone structures to deteriorate. In this work we have analysed samples from two modern limestone monuments in Rome, the Botticino surfaces of the ‘Vittoriano’ (by G.Sacconi, 1885-1911- Piazza Venezia) and the travertine basement of the ‘Statua dello Studente’ (by A.Cataldi, 1920- University city, La Sapienza), and focussed our investigation on the chemical composition of the copper-stained zones using XPS (X-ray Photoelectron Spectroscopy) as a surface-specific technique. Based on observations reporting on the structure and bonding at the calcite surfaces we have identified copper complexes and mixed calcium/copper carbonates associated with the stains, as well as the chemical state of other elements therein included, and related the compositional changes with differences in chromatic characteristics and sampling locations. PMID:22594435

  6. XPS characterization of (copper-based) coloured stains formed on limestone surfaces of outdoor Roman monuments.

    PubMed

    Salvi, Anna Maria; Langerame, Fausto; Macchia, Andrea; Sammartino, Maria Pia; Tabasso, Marisa Laurenzi

    2012-01-01

    Limestone basements holding bronzes or other copper alloys artefacts such as sculptures, decorations and dedicatory inscriptions are frequently met both in modern and ancient monuments. In outdoor conditions, such a combination implies the corrosion products of the copper based alloy, directly exposed to rainwater, will be drained off and migrate through the porous surfaces, forming stains of different colours and intensities, finally causing the limestone structures to deteriorate.In this work we have analysed samples from two modern limestone monuments in Rome, the Botticino surfaces of the 'Vittoriano' (by G.Sacconi, 1885-1911- Piazza Venezia) and the travertine basement of the 'Statua dello Studente' (by A.Cataldi, 1920- University city, La Sapienza), and focussed our investigation on the chemical composition of the copper-stained zones using XPS (X-ray Photoelectron Spectroscopy) as a surface-specific technique.Based on observations reporting on the structure and bonding at the calcite surfaces we have identified copper complexes and mixed calcium/copper carbonates associated with the stains, as well as the chemical state of other elements therein included, and related the compositional changes with differences in chromatic characteristics and sampling locations. PMID:22594435

  7. FTIR and XPS studies of surface chemistry of pyrite in flotation

    SciTech Connect

    Leppinen, J.; Laajalehto, K.; Kartio, I.; Suoninen, E.

    1995-12-31

    Efficient separation of pyrite is of great importance for the metallurgical performance of flotation processes. Presently, separation of pyrite by flotation is becoming more and more important for reduction of sulfur in coal. In this work Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) were used to study the surface chemistry of pyrite in depression, activation and xanthate adsorption under conditions of controlled potential. Modifications of pyrite surfaces after treatment with depressants (lime, sulfur dioxide, sodium cyanide) and after activation with metal ions (Cu, Pb) were studied. The principal adsorption product identified on pyrite was dixanthogen whose formation started at about +0.15 V and +0.25 V (vs, SHE) in ethyl and amyl xanthate solutions, respectively. Copper xanthate was formed on copper(II) activated pyrite. Activation mechanism of pyrite by copper(II) salts is likely to be electrochemical where copper occurs as copper(I) on the surface of pyrite. Effective depression is achieved by sulfur dioxide and sodium cyanide. Depression at high pH is due to formation of iron(III) hydroxides. Calcium ions do not affect the electrochemistry but adsorb on pyrite and reduce the surface sites for dixanthogen adsorption.

  8. XPS and STM studies of the oxidation of hydrogen chloride at Cu(100) surfaces

    NASA Astrophysics Data System (ADS)

    Altass, Hatem; Carley, Albert F.; Davies, Philip R.; Davies, Robert J.

    2016-08-01

    The dissociative chemisorption of HCl on clean and oxidized Cu(100) surfaces has been investigated using x-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Whereas the dissociation of HCl at the clean surface is limited to the formation of a (√ 2 × √ 2)-R45° Cl(a) monolayer, the presence of surface oxygen removes this barrier, leading to chlorine coverages up to twice that obtained at the clean surface. Additional features in the STM images that appear at these coverages are tentatively assigned to the nucleation of CuCl islands. The rate of reaction of the HCl was slightly higher on the oxidized surface but unaffected by the initial oxygen concentration or the availability of clean copper sites. Of the two distinct domains of adsorbed oxygen identified at room temperature on the Cu(100) surfaces, the (√ 2 × √ 2)-R45° structure reacts slightly faster with HCl than the missing row (√ 2 × 2 √ 2)-R45° O(a) structure. The results address the first stages in the formation of a copper chloride and present an interesting comparison with the HCl/O(a) reaction at Cu(110) surfaces, where oxygen also increased the extent of HCl reactions. The results emphasize the importance of the exothermic reaction to form water in the HCl/O(a) reaction on copper.

  9. The nature of nitrate at the ice surface studied by XPS and NEXAFS.

    PubMed

    Krepelová, Adéla; Newberg, John; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

    2010-08-21

    Trace contaminants such as strong acids have been suggested to affect the thickness of the quasi-liquid layer at the ice/air interface, which is at the heart of heterogeneous chemical reactions between snowpacks or cirrus clouds and the surrounding air. We used X-ray photoelectron spectroscopy (XPS) and electron yield near edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Advanced Light Source (ALS) to probe the ice surface in the presence of HNO(3) formed from the heterogeneous hydrolysis of NO(2) at 230 K. We studied the nature of the adsorbed species at the ice/vapor interfaces as well as the effect of HNO(3) on the hydrogen bonding environment at the ice surface. The NEXAFS spectrum of ice with adsorbed HNO(3) can be represented as linear combination of the clean ice and nitrate solution spectrum, thus indicating that in the presence of HNO(3) the ice surface consists of a mixture of clean ice and nitrate ions that are coordinated as in a concentrated solution at the same temperature but higher HNO(3) pressures. PMID:20532376

  10. The nature of nitrate at the ice surface studied by XPS and NEXAFS.

    PubMed

    Krepelová, Adéla; Newberg, John; Huthwelker, Thomas; Bluhm, Hendrik; Ammann, Markus

    2010-08-21

    Trace contaminants such as strong acids have been suggested to affect the thickness of the quasi-liquid layer at the ice/air interface, which is at the heart of heterogeneous chemical reactions between snowpacks or cirrus clouds and the surrounding air. We used X-ray photoelectron spectroscopy (XPS) and electron yield near edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Advanced Light Source (ALS) to probe the ice surface in the presence of HNO(3) formed from the heterogeneous hydrolysis of NO(2) at 230 K. We studied the nature of the adsorbed species at the ice/vapor interfaces as well as the effect of HNO(3) on the hydrogen bonding environment at the ice surface. The NEXAFS spectrum of ice with adsorbed HNO(3) can be represented as linear combination of the clean ice and nitrate solution spectrum, thus indicating that in the presence of HNO(3) the ice surface consists of a mixture of clean ice and nitrate ions that are coordinated as in a concentrated solution at the same temperature but higher HNO(3) pressures.

  11. XPS analysis of 440C steel surfaces lubricated with perfluoropolyethers under sliding conditions in high vacuum

    NASA Technical Reports Server (NTRS)

    Herrera-Fierro, Pilar; Masuko, Masabumi; Jones, William R., Jr.; Pepper, Stephen V.

    1994-01-01

    This work presents the results of the X-Ray Photoelectron Spectroscopy (XPS) analysis of AISI 440C ball surfaces lubricated with perfluoropolyether (PFPE) oils after friction experiments under sliding conditions at high load in air and vacuum environments. The PFPE lubricants tested were Demnum S100, Fomblin Z-25, and Krytox 143AB. It was found that all the PFPE lubricants were degraded by sliding contact causing the formation of inorganic fluorides on the metallic surfaces and a layer of organic decomposition products. KRYTOX 143AB was the least reactive of the three lubricants tested. It was also found that metal fluoride formed at off-scar areas. This suggests the formation of reactive species, such as COF2 or R(sub f)COF, during sliding experiments, which can diffuse through the lubricant film and react with the metallic surfaces away from the contact region. Comparison of reference specimens before sliding with those that had undergone the sliding tests showed that the amount of non-degraded PFPE remaining on the surface of the balls after the sliding experiments was greater than that of the balls without sliding.

  12. Chemical and structural characterization of Zrsbnd Csbnd Nsbnd Ag coatings: XPS, XRD and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Calderon V, S.; Cavaleiro, A.; Carvalho, S.

    2015-08-01

    In this report Zrsbnd Csbnd Nsbnd Ag coatings produced by dual magnetron sputtering are characterized by X-ray photoelectron spectroscopy (XPS) and complemented by X-ray diffraction, scanning electron microscopy, electron-probe microanalysis and Raman spectroscopy, in order to determine the chemical bonds and phases formed during the production process. The results demonstrate the possibility of producing coatings with different silver content (0-16 at.%), in which zirconium carbonitrides (70-95 at.%), amorphous carbon nitride phases (0-16 at.%) and residual zirconium oxide phases (∼5 at.%) coexists with the metallic silver. The profile analysis evidenced a highly oxidized surface due to the affinity of Zr to form ZrO2, and silver segregation to the surface. The composition after Ar+ bombardment revealed the contribution of silver clusters and metallic silver, together with the mentioned phases that vary in content depending on the deposition parameters utilized. STEM images revealed silver nanoparticles distributed in the Zrsbnd Csbnd N matrix with sizes around 5-20 nm, as well as silver surface agglomeration with sizes <80 nm.

  13. IR and XPS study of NO and CO interaction with palladium catalysts supported on aluminosilicates

    SciTech Connect

    Venezia, A.M.; Liotta, L.F.; Deganello, G. |; Terreros, P.; Pena, M.A.; Fierro, J.L.G.

    1999-02-16

    Adsorption of CO and NO individually and as a mixture of both on palladium catalysts has been investigated by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The effect of sodium ions has been considered by comparing Pd/SiO{sub 2} catalyst, sodium-doped Pd/SiO{sub 2}, and Pd on natural and synthetic silicoaluminates containing sodium in their bulk structure but differing in the surface area of the support. The presence of sodium induces a different adsorption behavior depending on its location, either at the surface of the catalysts or inside the support structure. As a consequence, different species are formed from the reaction between NO and CO at room temperature and at high temperature. Modification of the metal surface of the various catalysts is observed upon the gas treatments. Palladium is oxidized to a certain extent depending on the type of the catalyst support. Moreover, different chemical states of the adsorbed nitrogen species are found.

  14. An Application for Near Real-time Analysis of XPS Data

    SciTech Connect

    Lea, Alan S.; Swanson, Kenneth R.; Haack, Jereme N.; Castle, James E.; Tougaard, Sven M.; Baer, Donald R.

    2010-04-22

    Real-time analysis of x-ray photoelectron spectroscopy (XPS) data has significant potential advantages to scientists and analysts in that it has the potential to qualitatively alter the way an experiment is carried forward. As an example, immediate information about the magnitude of contamination and the layering of the surface could allow the scientist to immediately ask the next level of question and quickly re-direct the next experiment or test, even before the sample has been removed from the spectrometer. In addition to changing the nature of possible experiments, the immediate automated analysis of relatively simple procedures that an operator would normally conduct manually after the data files are saved, the report generation summarizing these analyses, and saving of this report to files with the critical metadata attached, has the potential to improve the turn-around time for data analysis, increase the sophistication of data analysis reportable to the scientist and reduce the labor involved in data analysis, resulting in significant time and cost savings.

  15. Chemistry characterization of jet aircraft engine particulate matter by XPS: Results from APEX III

    NASA Astrophysics Data System (ADS)

    Vander Wal, Randy L.; Bryg, Victoria M.; Huang, Chung-Hsuan

    2016-09-01

    This paper reports X-ray photoelectron spectroscopy (XPS) analysis of jet exhaust particulate matter (PM) from a B737, Lear, ERJ and A300 aircraft during the APEX III NASA led field campaign. Carbon hybridization and bonding chemistry are identified by high-resolution scans about the C1s core-shell region. Significant organic content as gauged by the sp3/sp2 ratio is found across engines and powers. Polar oxygen functional groups include carboxylic, carbonyl and phenol with combined content of 20% or more. By survey scans various elements including transition metals are identified along with lighter elements such as S, N and O in the form of oxides. Additives within lubricants are probable sources of Na, Ba, Ca, Zn, P and possibly Sn. Elements present and their percentages varied significantly across all engines, not revealing any trend or identifiable cause for the differences, though the origin is likely the same for the same element when observed. This finding suggests that their collective presence could serve as an environmental tracer for identifying PM originating from aircraft engines and serving as a diagnostic for engine performance and wear.

  16. Photoelectron interference fringes by super intense x-ray laser pulses

    NASA Astrophysics Data System (ADS)

    Toyota, Koudai; Tolstikhin, Oleg I.; Morishita, Toru; Watanabe, Shinichi

    2009-09-01

    The photoelectron spectra of H- produced by circularly polarized strong high-frequency laser pulses are theoretically studied. An oscillating substructure in the above-threshold ionization (ATI) peaks is observed, which extends the validity of the earlier findings in the 1D calculations [K. Toyota et al., Phys. Rev. A 76, 043418 (2007)] and 3D calculations for linear polarization [O. I. Tolstikhin, Phys. Rev. A 77, 032712 (2008)]. Its origin is due to an interference between a pair of photoelectron wave packets created in the rising and falling part of the pulse, which appears clearly in the stabilization regime.

  17. Effective cleaning of oil-protected bearing steel examined by XPS analysis. Part 2: Low pollution cleaning

    NASA Astrophysics Data System (ADS)

    Nishimura, Makoto; Minami, Masami; Matsui, Akihiko

    1991-04-01

    A cleaning procedure for ball bearings was developed which has a low possibility for environmental pollution. Both a commercially-available synthetic detergent and a potassium fatty acid (27 percent solution) were tested to determine their ability to clean bearing balls protected by an anti-rust oil containing barium sulfonate and zinc sulfonate. Results were compared. An X-ray photoelectron spectroscopy (XPS) analysis was performed to evaluate their effectiveness. Results showed that a synthetic detergent ultrasonic cleaning followed by an ethanol completely cleaned a mirror-finished surface, but not a turned one (Rmax: 20 microns). It was additionally determined that the potassium fatty acid solution exhibited superior cleaning capability when compared with organic solvents, including trichloroethylene, although the potassium fatty acid solution was inferior to the alkaline detergents.

  18. XPS study of the room temperature surface oxidation of zirconium and its binary alloys with tin, chromium and iron

    NASA Astrophysics Data System (ADS)

    Kumar, Lalit; Sarma, D. D.; Krummacher, S.

    1988-07-01

    Surface oxidation of pure zirconium and its dilute binary alloys with tin, chromium and iron has been investigated by X-ray photoelectron spectroscopy with a view to comparing their oxidation behaviour at room temperature. Mostly suboxides of zirconium are formed during the initial stages of oxidation at oxygen exposures < 10 L, while at higher exposures ZrO 2 is the dominant oxide species formed together with two suboxides. The relative XPS intensity of these two suboxides shows a broad and weak maximum in the exposure range 20-30 L. Pure zirconium as well as its dilute alloys exhibit a decreasing rate of oxidation with increasing oxygen exposures. No significant difference is observed in the surface oxidation behaviour of pure zirconium and its dilute binary alloys at room temperature.

  19. X-ray photoelectron spectroscopy as a probe of rhodium-ligand interaction in ionic liquids

    NASA Astrophysics Data System (ADS)

    Men, Shuang; Lovelock, Kevin R. J.; Licence, Peter

    2016-02-01

    We use X-ray photoelectron spectroscopy (XPS) to identify the interaction between the rhodium atom and phosphine ligands in six 1-octyl-3-methylimidazolium-based ionic liquids ([C8C1Im][X]). The formation of a mono-phosphine rhodium complex based upon addition of triphenylphosphine (PPh3) is confirmed by XPS in all ionic liquids studied herein. Due to the electron donation effect of the ligand, the rhodium atom becomes more negatively charged and thus exhibits a lower measured binding energy. The influence of the anion basicity on the formation of different types of rhodium complexes is also investigated. By introducing a biphosphine ligand, a chelated diphosphine rhodium complex is formed in ionic liquids with more basic anions and verified by both XPS and Infrared Spectroscopy (IR). The measured Rh 3d binding energies are correlated to the reaction selectivity of a hydroformylation reaction which inspires a method to design a metal catalyst to control the chemical reaction towards desired products in the future.

  20. A Cryo-XPS Study of Triammonium Citrate-KAuCl4-Na2SO3 Electroplating Solutions for Pb-Free Solder Packaging

    NASA Astrophysics Data System (ADS)

    Dalili, Neda; He, Anqiang; Liu, Qi; Ivey, Douglas G.

    2010-09-01

    Cyanide-free Au plating baths, containing KAuCl4, triammonium citrate, and sodium sulfite, have been developed by the authors. The stability of these solutions depends on the order of mixing of the additives. The aim of this study was to employ turbidity measurements and cryogenic x-ray photoelectron spectroscopy (XPS) to identify the role of the additives and the complexes responsible for solution stability or degradation. Electron microscopy was used to characterize any precipitation products generated in the solutions. It was shown that the long-term stability of the solutions is due to the role of citrate and sulfite as complexing agents.

  1. ToF-SIMS and XPS study of ancient papers

    NASA Astrophysics Data System (ADS)

    Benetti, Francesca; Marchettini, Nadia; Atrei, Andrea

    2011-01-01

    The surface composition of 18th century papers was investigated by means of ToF-SIMS and XPS. The aim of the present study was to explore the possibility of using these surface sensitive methods to obtain information which can help to determine the manufacturing process, provenance and state of conservation of ancient papers. The ToF-SIMS results indicate that the analyzed papers were sized by gelatin and that alum was added as hardening agent. The paper sheets produced in near geographical areas but in different paper mills exhibit a similar surface composition and morphology of the fibers as shown by the ToF-SIMS measurements. The ToF-SIMS and the XPS results indicate that a significant fraction of the cellulose fibers is not covered by the gelatin layer. This was observed for the ancient papers and for a modern handmade paper manufactured according to the old recipes.

  2. Sensitivity of photoelectron energy loss spectroscopy to surface reconstruction of microcrystalline diamond films

    NASA Astrophysics Data System (ADS)

    David, Denis G. F.; Pinault-Thaury, Marie-Amandine; Ballutaud, Dominique; Godet, Christian

    2013-05-01

    In X-ray Photoelectron Spectroscopy (XPS), binding energies and intensities of core level peaks are commonly used for chemical analysis of solid surfaces, after subtraction of a background signal. This background due to photoelectron energy losses to electronic excitations in the solid (surface and bulk plasmon excitation, inter band transitions) contains valuable information related to the near surface dielectric function ɛ(ħω). In this work, the sensitivity of Photoelectron Energy Loss Spectroscopy (PEELS) is investigated using a model system, namely the well-controlled surface reconstruction of diamond. Boron-doped microcrystalline thin films with a mixture of (1 1 1) and (1 0 0) preferential orientations were characterized in the as-grown state, with a partially hydrogenated surface, and after annealing at 1150 °C in ultra high vacuum. After annealing, the bulk (σ + π) plasmon of diamond at 34.5 eV is weakly attenuated but no evidence for surface graphitization is observed near 6 eV, as confirmed by electronic properties. Unexpected features which appear at 10 ± 1 eV and 19 ± 1 eV in the energy loss distribution are well described by simulation of surface plasmon excitations in graphite-like materials; alternatively, they also coincide with experimental inter band transition losses in some graphene layers. This comparative study shows that the PEELS technique gives a clear signature of weak effects in the diamond surface reconstruction, even in the absence of graphitization. It confirms the sensitivity of PEELS acquisition with standard XPS equipment as a complementary tool for surface analysis.

  3. Duplex Oxide Formation during Transient Oxidation of Cu-5%Ni(001) Investigated by In situ UHV-TEM and XPS

    SciTech Connect

    Yang, J.C.; Starr, D.; Kang, Y.; Luo, L.; Tong, X.; Zhou, G.

    2012-05-20

    The transient oxidation stage of a model metal alloy thin film was characterized with in situ ultra-high vacuum (UHV) transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and analytic high-resolution TEM. We observed the formations of nanosized NiO and Cu{sub 2}O islands when Cu-5a5%Ni(100) was exposed to oxygen partial pressure, pO{sub 2} = 1 x 10{sup -4} Torr and various temperatures in situ. At 350 C epitaxial Cu{sub 2}O islands formed initially and then NiO islands appeared on the surface of the Cu{sub 2}O island, whereas at 750 C NiO appeared first. XPS and TEM was used to reveal a sequential formation of NiO and then Cu{sub 2}O islands at 550 C. The temperature-dependant oxide selection may be due to an increase of the diffusivity of Ni in Cu with increasing temperature.

  4. Electrochemical oxidation of the chalcopyrite surface: an XPS and AFM study in solution at pH 4

    NASA Astrophysics Data System (ADS)

    Farquhar, Morag L.; Wincott, Paul L.; Wogelius, Roy A.; Vaughan, David J.

    2003-09-01

    The electrochemical oxidation of chalcopyrite (CuFeS 2) has been studied at pH 4 using voltammetry, coulometry, X-ray photoelectron spectroscopy (XPS) and both ex situ and in situ atomic force microscopy (AFM). Between 500 and 650 mV an anodic oxidation peak is observed, prior to the onset of the main decomposition reactions. Chalcopyrite electrodes in contact with electrolyte show some release of Cu into solution even without an applied potential. At 500 and 650 mV, the loss of Cu from the surface increases by a factor of 2 and 6, respectively. Oxidation at 500 mV results in the formation of a mixed oxide or hydroxide of iron, coincident with islands (<0.15 μm wide) of reaction products observed on the surface using AFM. The surface coverage of these islands increases with amount of charge passed. Oxidation at 650 mV shows similar processes have occurred, but with a greater island surface coverage and a more deeply altered surface. XPS depth profiling suggests iron oxide or hydroxide is now a major phase in the top ˜40 Å, with significant sulphate also formed. Observation of islands (alteration products) using in situ AFM under potential control shows that these features are not an artefact of the preparation methods.

  5. An XPS, TEM, and TPD study of the oxidation and ammoxidation of propene using mixed Fe-Sb oxide catalysts

    SciTech Connect

    Allen, M.D.; Poulston, S.; Bowker, M.

    1996-09-15

    Two mixed Fe-Sb oxide catalysts were investigated for the selective oxidation of propene to acrolein and the ammoxidation of propene in the presence of ammonia to acrylonitrile. The techniques used were chiefly X-ray photoelectron spectroscopy (XPS), temperature deprogrammed desorption (TPD), X-ray diffraction, and transmission electron microscopy. After propene dosing TPD experiments were carried out in the absence of gas phase oxygen utilising lattice oxygen for oxidation. The samples contained a 1:1 and 2:1 atomic ratio of Sb:Fe (referred to as SbFe and Sb2Fe, respectively). XPS data indicate that the surface has an antimony oxide enriched selvedge which favours the selective ammoxidation of propene. The Sb enriched surface of SbFe was found to be highly reducible in low pressures of ammonia, yielding a metallic antimony overlayer. Subsequent thermal desorption of this metal coating revealed a surface with an increased iron (III) oxide content which was not so easily reduced and found to be of a lower selectivity to partial ammoxidation products. The Sb2Fe sample was more stable towards reduction. 28 refs., 14 figs., 1 tab.

  6. Structural model of homogeneous As–S glasses derived from Raman spectroscopy and high-resolution XPS

    SciTech Connect

    Golovchak, R.; Shpotyuk, O.; Mccloy, J. S.; Riley, B. J.; Windisch, C. F.; Sundaram, S. K.; Kovalskiy, A.; Jain, H.

    2010-11-28

    The structure of homogeneous bulk As x S100- x (25 ≤ x ≤ 42) glasses, prepared by the conventional rocking–melting–quenching method, was investigated using high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. It is shown that the main building blocks of their glass networks are regular AsS3/2 pyramids and sulfur chains. In the S-rich domain, the existence of quasi-tetrahedral (QT) S = As(S1/2)3 units is deduced from XPS data, but with a concentration not exceeding ~3–5% of total atomic sites. Therefore, QT units do not appear as primary building blocks of the glass backbone in these materials, and an optimally-constrained network may not be an appropriate description for glasses when x < 40. Finally, it is shown that, in contrast to Se-based glasses, the ‘chain-crossing’ model is only partially applicable to sulfide glasses.

  7. Evaluation of the surface properties of PTFE foam coating filter media using XPS and contact angle measurements

    NASA Astrophysics Data System (ADS)

    Park, Byung Hyun; Lee, Myong-Hwa; Kim, Sang Bum; Jo, Young Min

    2011-02-01

    A newly developed PTFE foam coating filter was developed which can be used for hot gas cleaning at temperatures up to 250 °C. The emulsion-type PTFE was coated onto a woven glass fiber using a foam coating method. The filter surface was closely examined using X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The XPS results were used to determine the binding force between the carbon and fluorine of PTFE, which imparts coating stability to the filter medium. More than 95% of the bonds of the PTFE foam coating filter were between carbon and fluorine, and this filter demonstrated excellent hydrophobic and good oleophobic properties at the same time. The contact angles of liquid droplets on the filter surface were used to predict the potential wetability of the filter against water or oil. In addition, the very low surface free energy of the filter medium, which was evaluated using the Owens-Wendt method, demonstrates a very stable surface and a high de-dusting quality.

  8. Ultrafast photoelectron spectroscopy of solutions: space-charge effect

    NASA Astrophysics Data System (ADS)

    Al-Obaidi, R.; Wilke, M.; Borgwardt, M.; Metje, J.; Moguilevski, A.; Engel, N.; Tolksdorf, D.; Raheem, A.; Kampen, T.; Mähl, S.; Kiyan, I. Yu; Aziz, E. F.

    2015-09-01

    The method of time-resolved XUV photoelectron spectroscopy is applied in a pump-probe experiment on a liquid micro-jet. We investigate how the XUV energy spectra of photoelectrons are influenced by the space charge created due to ionization of the liquid medium by the pump laser pulse. XUV light from high-order harmonic generation is used to probe the electron population of the valence shell of iron hexacyanide in water. By exposing the sample to a short UV pump pulse of 266 nm wavelength and ˜55 fs duration, we observe an energy shift of the spectral component associated with XUV ionization from the Fe 3d(t2g) orbital as well as a shift of the water spectrum. Depending on the sequence of the pump and probe pulses, the arising energy shift of photoelectrons acquires a positive or negative value. It exhibits a sharp positive peak at small time delays, which facilitates to determine the temporal overlap between pump and probe pulses. The negative spectral shift is due to positive charge accumulated in the liquid medium during ionization. Its dissipation is found to occur on a (sub)nanosecond time scale and has a biexponential character. A simple mean-field model is provided to interpret the observations. A comparison between the intensity dependencies of the spectral shift and the UV ionization yield shows that the space-charge effect can be significantly reduced when the pump intensity is attenuated below the saturation level of water ionization. For the given experimental conditions, the saturation intensity lies at 6× {10}10 W cm-2.

  9. Transport of Photoelectrons in the Nightside Magnetosphere

    NASA Technical Reports Server (NTRS)

    Khazanov, G. V.; Liemohn, M. W.

    2002-01-01

    Kinetic modeling results are analyzed to examine the transport of photoelectrons through the nightside inner magnetosphere. Two sources are considered, those on the dayside from direct solar illumination and those across the nightside from light scattered by the upper atmosphere and geocorona. A natural filter exists on the nightside for the dayside photoelectrons. Coulomb collisions erode the distribution at low energies and low L shells, and magnetospheric convection compresses the electrons as they drift toward dawn. It is shown that for low-activity levels a band of photoelectrons forms between L = 4 and 6 that extends throughout the nightside local times and into the morning sector. For the scattered light photoelectrons the trapped zone throughout the nightside is populated with electrons of E less than 30 eV. At high L shells near dawn, convective compression on the nightside yields an accelerated population with electrons at energies up to twice the ionospheric energy maximum (that is, roughly 1200 eV for dayside photoelectrons and 60 eV for scattered light electrons). Modeled energy and pitch angle distributions are presented to show the features of these populations.

  10. Graphene defect formation by extreme ultraviolet generated photoelectrons

    SciTech Connect

    Gao, A. Lee, C. J.; Bijkerk, F.

    2014-08-07

    We have studied the effect of photoelectrons on defect formation in graphene during extreme ultraviolet (EUV) irradiation. Assuming the major role of these low energy electrons, we have mimicked the process by using low energy primary electrons. Graphene is irradiated by an electron beam with energy lower than 80 eV. After e-beam irradiation, it is found that the D peak, I(D), appears in the Raman spectrum, indicating defect formation in graphene. The evolution of I(D)/I(G) follows the amorphization trajectory with increasing irradiation dose, indicating that graphene goes through a transformation from microcrystalline to nanocrystalline and then further to amorphous carbon. Further, irradiation of graphene with increased water partial pressure does not significantly change the Raman spectra, which suggests that, in the extremely low energy range, e-beam induced chemical reactions between residual water and graphene are not the dominant mechanism driving defect formation in graphene. Single layer graphene, partially suspended over holes was irradiated with EUV radiation. By comparing with the Raman results from e-beam irradiation, it is concluded that the photoelectrons, especially those from the valence band, contribute to defect formation in graphene during irradiation.

  11. Photoelectron Emission Studies in CsBr at 257 nm

    SciTech Connect

    Maldonado, Juan R.; Liu, Zhi; Sun, Yun; Pianetta, Piero A.; Pease, Fabian W.; /Stanford U., Elect. Eng. Dept. /SLAC, SSRL

    2006-09-28

    CsBr/Cr photocathodes were found [1,2] to meet the requirements of a multi-electron beam lithography system operating with a light energy of 4.8 eV (257nm). The fact that photoemission was observed with a light energy below the reported 7.3 eV band gap for CsBr was not understood. This paper presents experimental results on the presence of intra-band gap absorption sites (IBAS) in CsBr thin film photo electron emitters, and presents a model based on IBAS to explain the observed photoelectron emission behavior at energies below band gap. A fluorescence band centered at 330 nm with a FWHM of about 0.34 eV was observed in CsBr/Cr samples under 257 nm laser illumination which can be attributed to IBAS and agrees well with previously obtained synchrotron photoelectron spectra[1] from the valence band of CsBr films.

  12. Photoelectron diffraction of magnetic ultrathin films: Fe/Cu(001)

    SciTech Connect

    Tobin, J.G. ); Wagner, M.K. . Dept. of Chemistry); Guo, X.Q.; Tong, S.Y. . Dept. of Physics)

    1991-01-03

    The preliminary results of an ongoing investigation of Fe/Cu(001) are presented here. Energy dependent photoelectron diffraction, including the spin-dependent variant using the multiplet split Fe3s state, is being used to investigate the nanoscale structures formed by near-monolayer deposits of Fe onto Cu(001). Core-level photoemission from the Fe3p and Fe3s states has been generated using synchrotron radiation as the tunable excitation source. Tentatively, a comparison of the experimental Fe3p cross section measurements with multiple scattering calculations indicates that the Fe is in a fourfold hollow site with a spacing of 3.6{Angstrom} between it and the atom directly beneath it, in the third layer. This is consistent with an FCC structure. The possibility of utilizing spin-dependent photoelectron diffraction to investigate magnetic ultrathin films will be demonstrated, using our preliminary spectra of the multiplet-split Fe3s os near-monolayer Fe/Cu(001). 18 refs., 10 figs.

  13. Scanning Photoelectron Microscope (SPEM) with a zone plate generated microprobe

    SciTech Connect

    Ade, H.; Kirz, J.; Hulbert, S.; Johnson, E.; Anderson, E.; Kern, D. . Dept. of Physics; Brookhaven National Lab., Upton, NY; Lawrence Berkeley Lab., CA . Center for X-Ray Optics; International Business Machines Corp., Yorktown Heights, NY . Thomas J. Watson Research Center)

    1989-01-01

    We describe instrumentation of a scanning photoelectron microscope (SPEM), which we are presently developing and commissioning at the X1A beamline of the National Synchrotron Light Source (NSLS). This instrument is designed to use the Soft X-ray Undulator (SXU) at the NSLS as a high brightness source to illuminate a Fresnel zone plate, thus forming a finely focused probe, {le} 0.2{mu}m in size, on the specimen surface. A grating monochromator selects the photon energy in the 400-800 eV range with an energy resolution better than 1 eV. The expected flux in the focus is in the 5 {times} 10{sup 7} {minus} 10{sup 9} photons/s range. A single pass Cylindrical Mirror Analyzer (CMA) is used to record photoemission spectra, or to form an image within a fixed electron energy bandwidth as the specimen is mechanically scanned. As a first test, a 1000 mesh Au grid was successfully imaged with Au 4 f primary photoelectrons, achieving a resolution of about 1{mu}m. 10 refs., 5 figs., 1 tab.

  14. Zero Kinetic Energy Photoelectron Spectroscopy of Benzo[h]quinoline.

    PubMed

    Harthcock, Colin; Zhang, Jie; Kong, Wei

    2015-12-17

    We report zero kinetic energy (ZEKE) photoelectron spectroscopy of benzo[h]quinoline (BhQ) via resonantly enhanced multiphoton ionization (REMPI) through the first electronically excited state S1. From the simulated REMPI spectra with and without Herzberg-Teller coupling, we conclude that vibronic coupling plays a minor but observable role in the electronic excitation to the S1 state. We further compare the S1 state of BhQ with the first two electronically excited states of phenanthrene, noticing a similarity of the S1 state of BhQ with the second electronically excited state S2 of phenanthrene. In the ZEKE spectra of BhQ, the vibrational frequencies of the cationic state D0 are consistently higher than those of the intermediate neutral state, indicating enhanced bonding upon ionization. The sparse ZEKE spectra, compared with the spectrum of phenanthrene containing rich vibronic activities, further imply that the nitrogen atom has attenuated the structural change between S1 and D0 states. We speculate that the nitrogen atom can withdraw an electron in the S1 state and donate an electron in the D0 state, thereby minimizing the structural change during ionization. The origin of the first electronically excited state is determined to be 29,410 ± 5 cm(-1), and the adiabatic ionization potential is determined to be 65,064 ± 7 cm(-1). PMID:26039927

  15. Probing keto-enol tautomerism using photoelectron spectroscopy.

    PubMed

    Capron, Nathalie; Casier, Bastien; Sisourat, Nicolas; Piancastelli, Maria Novella; Simon, Marc; Carniato, Stéphane

    2015-08-14

    We theoretically investigate the mechanism of tautomerism in the gas-phase acetylacetone molecule. The minimum energy path between the enolone and diketo forms has been computed using the Nudged-Elastic Band (NEB) method within the density-functional theory (DFT) using the projector augmented-wave method and generalized gradient approximation in Perdew-Wang (PW91) parametrization. The lowest transition state as well as several intermediate geometries between the two stable tautomers have been identified. The outer-valence ionization spectra for all determined geometries have been computed using the third-order non-Dyson algebraic diagrammatic construction technique. Furthermore, the oxygen core-shell ionization spectra for these geometries have been obtained using DFT and the Becke three-parameter Lee-Yang-Parr (B3LYP) functional. It is shown that all spectra depend strongly on the geometries demonstrating the possibility of following the proton-transfer dynamics using photoelectron spectroscopy in pump-probe experiments. PMID:26172609

  16. Coherent control of photoelectron wavepacket angular interferograms

    NASA Astrophysics Data System (ADS)

    Hockett, P.; Wollenhaupt, M.; Baumert, T.

    2015-11-01

    Coherent control over photoelectron wavepackets, via the use of polarization-shaped laser pulses, can be understood as a time and polarization-multiplexed process, where the final (time-integrated) observable coherently samples all instantaneous states of the light-matter interaction. In this work, we investigate this multiplexing via computation of the observable photoelectron angular interferograms resulting from multi-photon atomic ionization with polarization-shaped laser pulses. We consider the polarization sensitivity of both the instantaneous and cumulative continuum wavefunction; the nature of the coherent control over the resultant photoelectron interferogram is thus explored in detail. Based on this understanding, the use of coherent control with polarization-shaped pulses as a methodology for a highly multiplexed coherent quantum metrology is also investigated, and defined in terms of the information content of the observable.

  17. Acid generation efficiency: EUV photons versus photoelectrons

    NASA Astrophysics Data System (ADS)

    Goldfarb, Dario L.; Afzali-Ardakani, Ali; Glodde, Martin

    2016-03-01

    EUV photoacid generation efficiency has been described primarily in terms of the EUV photon absorption by the PAG or the resist matrix and the production of low energy photoelectrons, which are reported as being ultimately responsible for the high quantum efficiencies reported in EUV resists (<1). Such observation led to a number of recent studies on PAGs with variable electron affinity (EA) and reduction potential (Ered) presumably conducive to a differential EUV photoelectron harvesting efficiency. However, such studies either did not disclose the PAG chemical structures, replaced the EUV source with an e-beam source, or lacked a fundamental discussion of the underlying physical mechanisms behind EUV PAG decomposition. In this work, we report the EUV photospeed of a methacrylatebased resist formulated with a battery of openly disclosed isostructural sulfonium PAGs covering a wide range of EA's and Ered's, to unveil any preferential photoelectron scavenging effect. In parallel, several iodonium PAGs are also tested in order to compare the direct EUV photon absorption route to the photoelectron-based decomposition path. Contrarily to what has been widely reported, we have found no direct correlation whatsoever between photospeed and the calculated EA's or experimental Ered's for the isostructural sulfonium PAGs studied. Instead, we found that iodonium PAGs make more efficient use of the available EUV power due to their higher photoabsorption cross-section. Additionally, we determined a cation size effect for both PAG groups, which is able to further modulate the acid generation efficiency. Finally, we present a formal explanation for the unselective response towards photoelectron harvesting based on the stabilization of the PAG cation by bulky substituent groups, the spatial and temporal range of the transient photoelectron and the differences in electron transfer processes for the different systems studied.

  18. XPS and SIMS study of the surface and interface of aged C+ implanted uranium

    DOE PAGES

    Donald, Scott B.; Siekhaus, Wigbert J.; Nelson, Art J.

    2016-09-08

    X-ray photoelectron spectroscopy in combination with secondary ion mass spectrometry depth profiling were used to investigate the surface and interfacial chemistry of C+ ion implanted polycrystalline uranium subsequently oxidized in air for over 10 years at ambient temperature. The original implantation of 33 keV C+ ions into U238 with a dose of 4.3 × 1017 cm–3 produced a physically and chemically modified surface layer that was characterized and shown to initially prevent air oxidation and corrosion of the uranium after 1 year in air at ambient temperature. The aging of the surface and interfacial layers were examined by using themore » chemical shift of the U 4f, C 1s, and O 1s photoelectron lines. In addition, valence band spectra were used to explore the electronic structure of the aged carbide surface and interface layer. Moreover, the time-of-flight secondary ion mass spectrometry depth profiling results for the aged sample confirmed an oxidized uranium carbide layer over the carbide layer/U metal interface.« less

  19. Anion photoelectron imaging spectroscopy of glyoxal

    NASA Astrophysics Data System (ADS)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei

    2016-09-01

    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  20. Titan's photoelectron energy peaks: A statistical overview and comparison to Mars and Venus

    NASA Astrophysics Data System (ADS)

    Wellbrock, A.; Coates, A. J.; Jones, G. H.

    2014-04-01

    Cassini's CAPS Electron Spectrometer (ELS) has observed discrete energy peaks at 24.1 eV in the electron spectra in Titan's ionosphere. These electrons are believed to be photoelectrons generated due to the ionisation of N2 by the strong solar He II (30.4nm) line. They are generally observed in Titan's dayside ionosphere, because this is where neutral N2 particles can be ionized by solar radiation. Coates et al. (2007) discuss initial observations of these photoelectrons in Titan's distant tail during the Titan encounter 'T9'. Wellbrock et al. (2012) describe three other case studies where these photoelectrons were observed at large distances from Titan. The photoelectrons are unlikely to have originated at these locations because of low neutral N2 densities. The most likely explanation for their existence at these locations is that they travelled along magnetic field lines to the observation sites from the dayside ionosphere, where they were created. Hybrid modelling results support this idea (Wellbrock et al., 2012). We continue the study of photoelectron energy peaks at Titan here and present results from a statistical overview of observations in Titan's ionosphere and exosphere.Similar photoelectron energy peak observations at Mars and Venus due to the ionisation of CO2 and O have been studied (Frahm et al., 2006, Coates et al., 2008, 2011). We compare our results at Titan to such studies at Mars and Venus, and discuss implications on the ionospheric and exospheric morphology of these unmagnetised objects with an atmosphere. We also investigate how photoelectrons can be used as tracers of magnetic field lines in order to improve our understanding of these complex magnetic environments.

  1. In situ x-ray photoelectron spectroscopy studies of gas/solidinterfaces at near-ambient conditions

    SciTech Connect

    Bluhm, Hendrik; Havecker, Michael; Knop-Gericke, Axel; Kiskinova,Maya; Schlogl, Robert; Salmeron, Miquel

    2007-12-03

    X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst's chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, i.e., in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces.

  2. Conduction band offset at GeO{sub 2}/Ge interface determined by internal photoemission and charge-corrected x-ray photoelectron spectroscopies

    SciTech Connect

    Zhang, W. F.; Nishimula, T.; Nagashio, K.; Kita, K.; Toriumi, A.

    2013-03-11

    We report a consistent conduction band offset (CBO) at a GeO{sub 2}/Ge interface determined by internal photoemission spectroscopy (IPE) and charge-corrected X-ray photoelectron spectroscopy (XPS). IPE results showed that the CBO value was larger than 1.5 eV irrespective of metal electrode and substrate type variance, while an accurate determination of valence band offset (VBO) by XPS requires a careful correction of differential charging phenomena. The VBO value was determined to be 3.60 {+-} 0.2 eV by XPS after charge correction, thus yielding a CBO (1.60 {+-} 0.2 eV) in excellent agreement with the IPE results. Such a large CBO (>1.5 eV) confirmed here is promising in terms of using GeO{sub 2} as a potential passivation layer for future Ge-based scaled CMOS devices.

  3. Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

    SciTech Connect

    Imam, H.; Ahmed, Doaa; Eldakrouri, Ashraf

    2013-06-21

    The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all the different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.

  4. Elemental content of enamel and dentin after bleaching of teeth (a comparative study between laser-induced breakdown spectroscopy and x-ray photoelectron spectroscopy)

    NASA Astrophysics Data System (ADS)

    Imam, H.; Ahmed, Doaa; Eldakrouri, Ashraf

    2013-06-01

    The elemental content of the superficial and inner enamel as well as that of dentin was analyzed using laser-induced breakdown spectroscopy (LIBS) and x-ray photoelectron spectroscopy (XPS) of bleached and unbleached tooth specimens. It is thus clear from the spectral analysis using both the LIBS and XPS technique that elemental changes (though insignificant within the scopes of this study) of variable intensities do occur on the surface of the enamel and extend deeper to reach dentin. The results of the LIBS revealed a slight reduction in the calcium levels in the bleached compared to the control specimens in all the different bleaching groups and in both enamel and dentin. The good correlation found between the LIBS and XPS results demonstrates the possibility of LIBS technique for detection of minor loss in calcium and phosphorus in enamel and dentin.

  5. Assigning Oxidation States to Organic Compounds via Predictions from X-ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    SciTech Connect

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff H.; Linford, Matthew R.

    2014-02-11

    The traditional assignment of oxidation numbers to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation number of zero when bonded to carbon. Here we show that X-ray photoelectron spectroscopy (XPS), a core electron spectroscopy that is sensitive to oxidation states of elements, confirms his suggestion. In particular, in this work we: (i) list the typical rules for assigning oxidation numbers, (ii) discuss the traditional assignment of oxidation numbers to organic molecules, (iii) review Calzaferri’s solution, (iv) introduce X-ray photoelectron spectroscopy (XPS), (v) show the consistency of Calzaferri’s suggestion with XPS results, (vi) provide supporting examples from the literature, (vii) provide examples from our own research, and (viii) further confirm the Calzaferri suggestion/photoelectron spectroscopy results by discussing two organic well-known reactions. We end by reechoing Calzaferri’s suggestion that the traditional rules for assigning oxidation numbers to organic molecules be modified.

  6. X-Ray Photoelectron Spectroscopy Depth Profiling of Electrochemically Prepared Thin Oxide Layers on Duplex Stainless Steel

    NASA Astrophysics Data System (ADS)

    Donik, Črtomir; Kocijan, Aleksandra; Mandrino, Djordje; Jenko, Monika

    2011-10-01

    The surface oxidation of duplex stainless steel (DSS 2205) was studied by X-ray photoelectron spectroscopy (XPS). The experiments were performed on the alloy after controlled oxidation in a chloride-enriched solution at controlled potentials. The evolution of the passive film formed on the DSS in a chloride solution was studied using cyclic voltammetry with XPS surface characterization at selected potentials. The evolution of the oxide films and its specific compositions formed on the DSS was studied as a function of depth. Fe/Cr oxidized layers and oxide thicknesses were observed and correlated with the various potentiostatic potentials. The importance of Mo and Cr inside the oxide films in this article is studied and described, whereas their role in the protective layer, as oxides, is significant.

  7. X-ray photoelectron spectroscopy study on the chemistry involved in tin oxide film growth during chemical vapor deposition processes

    SciTech Connect

    Mannie, Gilbere J. A.; Gerritsen, Gijsbert; Abbenhuis, Hendrikus C. L.; Deelen, Joop van; Niemantsverdriet, J. W.; Thuene, Peter C.

    2013-01-15

    The chemistry of atmospheric pressure chemical vapor deposition (APCVD) processes is believed to be complex, and detailed reports on reaction mechanisms are scarce. Here, the authors investigated the reaction mechanism of monobutyl tinchloride (MBTC) and water during SnO{sub 2} thin film growth using x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). XPS results indicate an acid-base hydrolysis reaction mechanism, which is tested with multilayer experiments, demonstrating self-terminating growth. In-house developed TEM wafers are used to visualize nucleation during these multilayer experiments, and results are compared with TEM results of APCVD samples. Results show almost identical nucleation behavior implying that their growth mechanism is identical. Our experiments suggest that in APCVD, when using MBTC and water, SnO{sub 2} film growth occurs via a heterolytic bond splitting of the Sn-Cl bonds without the need to invoke gas-phase radical or coordination chemistry of the MBTC precursor.

  8. Thermal stability of electron-irradiated poly(tetrafluoroethylene) - X-ray photoelectron and mass spectroscopic study

    NASA Technical Reports Server (NTRS)

    Wheeler, Donald R.; Pepper, Stephen V.

    1990-01-01

    Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species were evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS spectrum that were associated with damage diminished, giving the appearance that the radiation damage had annealed. The observations were interpreted by incorporating mass transport of severed chain fragments and thermal decomposition of severely damaged material into the branched and cross-linked network model of irradiated PTFE. The apparent annealing of the radiation damage was due to covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

  9. X-ray photoelectron spectroscopy study of para-substituted benzoic acids chemisorbed to aluminum oxide thin films

    SciTech Connect

    Kreil, Justin; Ellingsworth, Edward; Szulczewski, Greg

    2013-11-15

    A series of para-substituted, halogenated (F, Cl, Br, and I) benzoic acid monolayers were prepared on the native oxide of aluminum surfaces by solution self-assembly and spin-coating techniques. The monolayers were characterized by x-ray photoelectron spectroscopy (XPS) and water contact angles. Several general trends are apparent. First, the polarity of the solvent is critical to monolayer formation. Protic polar solvents produced low coverage monolayers; in contrast, nonpolar solvents produced higher coverage monolayers. Second, solution deposition yields a higher surface coverage than spin coating. Third, the thickness of the monolayers determined from XPS suggests the plane of the aromatic ring is perpendicular to the surface with the carboxylate functional group most likely binding in a bidentate chelating geometry. Fourth, the saturation coverage (∼2.7 × 10{sup 14} molecules cm{sup −2}) is independent of the para-substituent.

  10. X-ray photoelectron spectroscopy as a probe of the interaction between rhodium acetate and ionic liquids

    NASA Astrophysics Data System (ADS)

    Men, Shuang; Jiang, Jing

    2016-02-01

    X-ray photoelectron spectroscopy (XPS) is used as a probe of the interaction between rhodium acetate ([Rh2(OAc)4]) and ionic liquids. Due to the impact of the anion of ionic liquids on the electronic environment of the rhodium centre, the measured Rh 3d binding energies of [Rh2(OAc)4] dissolved in a series of ionic liquids were found to decrease along with the increasing of the basicity of anions. The reduction of Rh(II) to Rh(0) in 1-octyl-3methylimidazolium acetate ([C8C1Im][OAc]) under UHV condition was monitored by XPS. The intensity of the new formed metallic Rh(0) peak was found increased along with time. The surface enrichment of the new formed Rh(0) species in the system was also concluded.

  11. An X-ray photoelectron spectroscopy study of the hydration of C{sub 2}S thin films

    SciTech Connect

    Rheinheimer, Vanessa; Casanova, Ignasi

    2014-06-01

    Electron-beam evaporation was used to produce thin films of β-dicalcium silicate. Chemical and mineralogical compositions were characterized by X-ray photoelectron spectroscopy (XPS) and grazing-angle X-ray diffraction (GAXRD), respectively. Results show that no fractionation occurs during evaporation and isostructural condensation of the material as synthesized films have the same composition as the initial bulk material. Samples were gradually hydrated under saturated water spray conditions and analyzed with XPS. Polymerization of the silicate chains due to hydration, and subsequent formation of C-S-H, has been monitored through evaluation of energy shifts on characteristic silicon peaks. Quantitative analyses show changes on the surface by the reduction of the Ca/Si ratio and an increase on the difference between binding energies of bridging and non-bridging oxygen. Finally, SEM/FIB observation shows clear differences between the surface and cross section of the initial sample and the reacted sample.

  12. Theoretical and experimental study of valence photoelectron spectrum of D,L-alanine amino acid.

    PubMed

    Farrokhpour, H; Fathi, F; De Brito, A Naves

    2012-07-01

    In this work, the He-I (21.218 eV) photoelectron spectrum of D,L-alanine in the gas phase is revisited experimentally and theoretically. To support the experiment, the high level ab initio calculations were used to calculate and assign the photoelectron spectra of the four most stable conformers of gaseous alanine, carefully. The symmetry adapted cluster/configuration interaction (SAC-CI) method based on single and double excitation operators (SD-R) and its more accurate version, termed general-R, was used to separately calculate the energies and intensities of the ionization bands of the L- and D-alanine conformers. The intensities of ionization bands were calculated based on the monopole approximation. Also, natural bonding orbital (NBO) calculations were employed for better spectral band assignment. The relative electronic energy, Gibbs free energy, and Boltzmann population ratio of the conformers were calculated at the experimental temperature (403 K) using several theoretical methods. The theoretical photoelectron spectrum of alanine was calculated by summing over the spectra of individual D and L conformers weighted by different population ratios. Finally, the population ratio of the four most stable conformers of alanine was estimated from the experimental photoelectron spectrum using theoretical calculations for the first time.

  13. Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

    SciTech Connect

    Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; Rani, Sana; Chang, Rui; Karlsson, Patrik G.; Edwards, Mårten O. M.; Lundqvist, Måns; Moberg, Robert; Ross, Phil; Hussain, Zahid; Liu, Zhi

    2015-05-07

    We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.

  14. Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface

    PubMed Central

    Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; Rani, Sana; Chang, Rui; Karlsson, Patrik G.; Edwards, Mårten O. M.; Lundqvist, Måns; Moberg, Robert; Ross, Phil; Hussain, Zahid; Liu, Zhi

    2015-01-01

    We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt2+ and Pt4+ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry. PMID:25950241

  15. Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

    DOE PAGES

    Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; Rani, Sana; Chang, Rui; Karlsson, Patrik G.; Edwards, Mårten O. M.; Lundqvist, Måns; Moberg, Robert; Ross, Phil; et al

    2015-05-07

    We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

  16. XPS study of nitrogen dioxide adsorption on metal oxide particle surfaces under different environmental conditions.

    PubMed

    Baltrusaitis, Jonas; Jayaweera, Pradeep M; Grassian, Vicki H

    2009-10-01

    The adsorption of nitrogen dioxide on gamma aluminium oxide (gamma-Al(2)O(3)) and alpha iron oxide (alpha-Fe(2)O(3)) particle surfaces under various conditions of relative humidity, presence of molecular oxygen and UV light has been investigated. X-Ray photoelectron spectroscopy (XPS) is used to monitor the different surface species that form under these environmental conditions. Adsorption of NO(2) on aluminum oxide particle surfaces results primarily in the formation of surface nitrate, NO(3)(-) with an oxidation state of +5, as indicated by a peak with binding energy of 407.3 eV in the N1s region. An additional minority species, sensitive to the presence of relative humidity and molecular oxygen, is also observed in the N1s region with lower binding energy of 405.9 eV. This peak is assigned to a surface species in the +4 oxidation state. When irradiated with UV light, other species form on the surface. These surface-bound photochemical products all have lower binding energy, between 400 and 402 eV, indicating reduced nitrogen species in the range of N oxidations states spanning +1 to -1. Co-adsorbed water decreases the amount of these reduced surface-bound products while the presence of molecular oxygen completely suppresses the formation of all reduced nitrogen species on aluminum oxide particle surfaces. For NO(2) on iron oxide particle surfaces, photoreduction is enhanced relative to gamma-Al(2)O(3) and surface bound photoreduced species are observed under all environmental conditions. Complementing the experimental data, N1s core electron binding energies (CEBEs) were calculated using DFT for a number of nitrogen-containing species in the gas phase and adsorbed on an Al(8)O(12) cluster. A range of CEBEs is calculated for various nitrogen species in different adsorption modes and oxidation states. These calculated values are discussed in light of the peaks observed in the XPS N1s region and the possible species that form following NO(2) adsorption and

  17. Composition and evolution of the solid-electrolyte interphase in Na2Ti3O7 electrodes for Na-ion batteries: XPS and Auger parameter analysis.

    PubMed

    Muñoz-Márquez, Miguel A; Zarrabeitia, Maider; Castillo-Martínez, Elizabeth; Eguía-Barrio, Aitor; Rojo, Teófilo; Casas-Cabanas, Montse

    2015-04-15

    Na2Ti3O7 is considered a promising negative electrode for Na-ion batteries; however, poor capacity retention has been reported and the stability of the solid-electrolyte interphase (SEI) could be one of the main actors of this underperformance. The composition and evolution of the SEI in Na2Ti3O7 electrodes is hereby studied by means of X-ray photoelectron spectroscopy (XPS). To overcome typical XPS limitations in the photoelectron energy assignments, the analysis of the Auger parameter is here proposed for the first time in battery materials characterization. We have found that the electrode/electrolyte interface formed upon discharge, mostly composed by carbonates and semicarbonates (Na2CO3, NaCO3R), fluorides (NaF), chlorides (NaCl) and poly(ethylene oxide)s, is unstable upon electrochemical cycling. Additionally, solid state nuclear magnetic resonance (NMR) studies prove the reaction of the polyvinylidene difluoride (PVdF) binder with sodium. The powerful approach used in this work, namely Auger parameter study, enables us to correctly determine the composition of the electrode surface layer without any interference from surface charging or absolute binding energy calibration effects. As a result, the suitability for Na-ion batteries of binders and electrolytes widely used for Li-ion batteries is questioned here.

  18. Composition and evolution of the solid-electrolyte interphase in Na2Ti3O7 electrodes for Na-ion batteries: XPS and Auger parameter analysis.

    PubMed

    Muñoz-Márquez, Miguel A; Zarrabeitia, Maider; Castillo-Martínez, Elizabeth; Eguía-Barrio, Aitor; Rojo, Teófilo; Casas-Cabanas, Montse

    2015-04-15

    Na2Ti3O7 is considered a promising negative electrode for Na-ion batteries; however, poor capacity retention has been reported and the stability of the solid-electrolyte interphase (SEI) could be one of the main actors of this underperformance. The composition and evolution of the SEI in Na2Ti3O7 electrodes is hereby studied by means of X-ray photoelectron spectroscopy (XPS). To overcome typical XPS limitations in the photoelectron energy assignments, the analysis of the Auger parameter is here proposed for the first time in battery materials characterization. We have found that the electrode/electrolyte interface formed upon discharge, mostly composed by carbonates and semicarbonates (Na2CO3, NaCO3R), fluorides (NaF), chlorides (NaCl) and poly(ethylene oxide)s, is unstable upon electrochemical cycling. Additionally, solid state nuclear magnetic resonance (NMR) studies prove the reaction of the polyvinylidene difluoride (PVdF) binder with sodium. The powerful approach used in this work, namely Auger parameter study, enables us to correctly determine the composition of the electrode surface layer without any interference from surface charging or absolute binding energy calibration effects. As a result, the suitability for Na-ion batteries of binders and electrolytes widely used for Li-ion batteries is questioned here. PMID:25811538

  19. Spatial resolution in vector potential photoelectron microscopy

    SciTech Connect

    Browning, R.

    2014-03-15

    The experimental spatial resolution of vector potential photoelectron microscopy is found to be much higher than expected because of the cancellation of one of the expected contributions to the point spread function. We present a new calculation of the spatial resolution with support from finite element ray tracing, and experimental results.

  20. Near threshold behavior of photoelectron satellite intensities

    SciTech Connect

    Shirley, D.A.; Becker, U.; Heimann, P.A.; Langer, B.

    1987-09-01

    The historical background and understanding of photoelectron satellite peaks is reviewed, using He(n), Ne(1s), Ne(2p), Ar(1s), and Ar(3s) as case studies. Threshold studies are emphasized. The classification of electron correlation effects as either ''intrinsic'' or ''dynamic'' is recommended. 30 refs., 7 figs.

  1. The vacuum ultraviolet photoelectron spectrum of difluoramine

    NASA Astrophysics Data System (ADS)

    Colbourne, D.; Frost, D. C.; McDowell, C. A.; Westwood, N. P. C.

    1980-06-01

    The HeI photoelectron spectrum of difluoramine is reported. The seven ionization potentials within the Hel region have been assigned. Extensive vibrational structure on the first band of both HNF 2 and DNF 2, and ab initio calculations of the ionic geometry, indicate that the ground ionic state is planar.

  2. Photoelectron Spectroscopy in Advanced Placement Chemistry

    ERIC Educational Resources Information Center

    Benigna, James

    2014-01-01

    Photoelectron spectroscopy (PES) is a new addition to the Advanced Placement (AP) Chemistry curriculum. This article explains the rationale for its inclusion, an overview of how the PES instrument records data, how the data can be analyzed, and how to include PES data in the course. Sample assessment items and analysis are included, as well as…

  3. [Vibrational spectrum and XPS contrastive studies on pyrochlore-type oxygen-rich Ce2Zr2O8 and oxygen-defective Nd2Zr2O7 phases].

    PubMed

    Xie, Hua; Wang, Lie-lin; Luo, De-li; Chen, Min

    2014-06-01

    Pyrochlore-type oxygen-rich Ce2Zr2O8 phase was prepared successfully by graphite reduction method. With the oxygen[U8]-defective Nd2Zr2O7 substituting for the oxidized precursor phase CeZrO3.5+Δ was carried out the structure comparative analysis with Ce2Zr2O8. The X-ray diffraction (XRD), Raman spectroscopy (Raman), infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) were used to characterize the crystal structure of samples. The XRD experimental results show that Ce2Zr2O8 bulk phase contains the typical structure of pyrochlore, the superstructure peaks that characterize Ce/Zr cations ordering arrangement are very obvious, but the Zr-O ligands had also transformed from octahedrons of the co-top connection in the precursor to cubes of co-edge connection in the Ce2Zr2O8, and the formation of [ZrO8] ligand reduced greatlly the structural stability of Ce2Zr2O8 phase. Raman and IR results show that vibrational spectra bands of Ce2Zr2O8 phase increased significantly, meaning that the enriched oxygen ions result in a removal of the degeneracy peak for Ce2Zr2O8 phase, which confirms further the structural symmetry of Ce2Zr2O8 phase lower than its precursor. XPS results show that Ce (IV) characteristic peak (916.3 eV) in the Ce2Zr2O8 phase surface is very obvious. No the appearance of Ce (III) peak (885 eV) suggests that Ce3+ from the precursor has been completely oxidized into Ce4+ in the Ce2Zr2O8 phase; the Zr(3d) binding energy is close to fluorite phase with Zr4+, which confirms that [ZrO8] ligand in the Ce2Zr2O8 surface is consistent with the bulk phase. The increasing low binding energy of O(1s) shows that oxygen species in the Ce2Zr2O8 bulk phase are between lattice oxygen and adsorbed oxygen, the presence of high oxygen peak suggests that the surface of Ce2Zr2O8 contains adsorbed oxygen, and the bonding strength between adsorption oxygen and Ce2Zr2O8 bulk phase is between CeO2 and Nd2Zr2O7. PMID:25358157

  4. Photoelectron spectroscopy and the dipole approximation

    SciTech Connect

    Hemmers, O.; Hansen, D.L.; Wang, H.

    1997-04-01

    Photoelectron spectroscopy is a powerful technique because it directly probes, via the measurement of photoelectron kinetic energies, orbital and band structure in valence and core levels in a wide variety of samples. The technique becomes even more powerful when it is performed in an angle-resolved mode, where photoelectrons are distinguished not only by their kinetic energy, but by their direction of emission as well. Determining the probability of electron ejection as a function of angle probes the different quantum-mechanical channels available to a photoemission process, because it is sensitive to phase differences among the channels. As a result, angle-resolved photoemission has been used successfully for many years to provide stringent tests of the understanding of basic physical processes underlying gas-phase and solid-state interactions with radiation. One mainstay in the application of angle-resolved photoelectron spectroscopy is the well-known electric-dipole approximation for photon interactions. In this simplification, all higher-order terms, such as those due to electric-quadrupole and magnetic-dipole interactions, are neglected. As the photon energy increases, however, effects beyond the dipole approximation become important. To best determine the range of validity of the dipole approximation, photoemission measurements on a simple atomic system, neon, where extra-atomic effects cannot play a role, were performed at BL 8.0. The measurements show that deviations from {open_quotes}dipole{close_quotes} expectations in angle-resolved valence photoemission are observable for photon energies down to at least 0.25 keV, and are quite significant at energies around 1 keV. From these results, it is clear that non-dipole angular-distribution effects may need to be considered in any application of angle-resolved photoelectron spectroscopy that uses x-ray photons of energies as low as a few hundred eV.

  5. Vibrationally resolved photoelectron imaging of Cu2H- and AgCuH- and theoretical calculations.

    PubMed

    Xie, Hua; Li, Xiaoyi; Zhao, Lijuan; Liu, Zhiling; Qin, Zhengbo; Wu, Xia; Tang, Zichao; Xing, Xiaopeng

    2013-02-28

    Vibrationally resolved photoelectron spectra have been obtained for Cu(2)H(-) and AgCuH(-) using photoelectron imaging at 355 nm. Two transition bands X and A are observed for each spectrum. The X bands in both spectra show the vibration progressions of the Cu-H stretching mode and the broad peaks of these progressions indicate significant structural changes from Cu(2)H(-) and AgCuH(-) to their neutral ground states. The A bands in the spectra of Cu(2)H(-) and CuAgH(-) show stretching progressions of Cu-Cu and Ag-Cu, respectively. The contours of these two progressions are pretty narrow, indicating relatively small structural changes from Cu(2)H(-) and AgCuH(-) to their neutral excited states. Calculations based on density functional theory indicate that the ground states of Cu(2)H(-) and AgCuH(-) and the first excited states of their neutrals are linear, whereas their neutral ground states are bent. The photoelectron detachment energies and vibrational frequencies from these calculations are in good agreement with the experimental observations. Especially, the theoretical predication of linear structures for the anions and the neutral excited states are supported by the spectral features of A bands, in which the bending modes are inactive. Comparisons among the vertical detachment energies of Cu(2)H(-), AgCuH(-), and their analogs help to elucidate electronic characteristics of coinage metal elements and hydrogen in small clusters.

  6. Photoelectron spectroscopy of liquid water, some alcohols, and pure nonane in free micro jets

    NASA Astrophysics Data System (ADS)

    Faubel, Manfred; Steiner, Björn; Toennies, J. Peter

    1997-06-01

    The recently developed technique of accessing volatile liquids in a high vacuum environment by using a very thin liquid jet is implemented to carry out the first measurements of photoelectron spectra of pure liquid water, methanol, ethanol, 1-propanol, 1-butanol, and benzyl alcohol as well as of liquid n-nonane. The apparatus, which consists of a commercial hemispherical (10 cm mean radius) electron analyzer and a hollow cathode discharge He I light source is described in detail and the problems of the sampling of the photoelectrons in such an environment are discussed. For water and most of the alcohols up to six different electronic bands could be resolved. The spectra of 1-butanol and n-nonane show two weakly discernable peaks from which the threshold ionization potential could be determined. A deconvolution of the photoelectron spectra is used to extract ionization potentials of individual molecular bands of molecules near the surface of the liquid and shifts of the order of 1 eV compared to the gas phase are observed. A molecular orientation for water molecules at the surface of liquid water is inferred from a comparison of the relative band strengths with the gas phase. Similar effects are also observed for some of the alcohols. The results are discussed in terms of a simple "Born-solvation" model.

  7. Carbonaceous matter in peridotites and basalts studied by XPS, SALI, and LEED

    SciTech Connect

    Tingle, T.N. SRI International, Menlo Park, CA ); Mathez, E.A. ); Hochella, M.F. Jr. )

    1991-05-01

    Carbonaceous matter in peridotite xenoliths and basalt from the Hualalai Volcano, in a basalt glass collected directly from an active lava lake on the east rift of Kilauea, in garnet and diopside megacrysts from the Jagersfontein kimberlite, and in gabbros from the Stillwater and Bushveld Complexes has been studied by X-ray photoelectron spectroscopy (XPS), thermal-desorption surface analysis by laser ionization (SALI), and low-energy electron diffraction (LEED). The basalt and two of the four xenoliths from Hualalai and both Jagersfontein megacrysts yielded trace quantities ({le}10 nanomoles) of organic compounds on heating to 700C. Organics were not detected in the rocks from the layered intrusions, and neither carbonaceous matter nor organics were detected in the glass from the lava lake. Where detected, organics appear to be associated with carbonaceous films on microcrack surfaces. Carbonaceous matter exists as films less than a few nm thick and particles up to 20 {mu}m across, both of which contain elements expected to be present in significant quantities in magmatic vapors, namely Si, alkalis, halogens, N, and transition metals. LEED studies suggest that the carbonaceous films are amorphous. The data suggest two possible mechanisms for the formation of the organics. One is that they are a product of abiotic heterogeneous catalysis of volcanic gas on new, chemically active mineral surfaces formed by fracturing during cooling. Alternatively, organics may have been assimilated into the volcanic gases prior to eruption and then deposited on cracks formed during eruption and cooling. In any case, there is no evidence to suggest that the organics represent laboratory or field biogenic contamination.

  8. Structural, XPS and magnetic studies of pulsed laser deposited Fe doped Eu{sub 2}O{sub 3} thin film

    SciTech Connect

    Kumar, Sandeep; Prakash, Ram; Choudhary, R.J.; Phase, D.M.

    2015-10-15

    Highlights: • Growth of Fe doped Eu{sub 2}O{sub 3} thin films by PLD. • XRD and Raman’s spectroscopy used for structure confirmation. • The electronic states of Eu and Fe are confirmed by XPS. • Magnetic properties reveals room temperature magnetic ordering in deposited film. - Abstract: Fe (4 at.%) doped europium (III) oxide thin film was deposited on silicon (1 0 0) substrate by pulsed laser deposition technique. Structural, spectral and magnetic properties were studied by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and magnetization measurements. XRD and Raman spectroscopy reveal that the grown film is single phased and belongs to the cubic structure of Eu{sub 2}O{sub 3}. XPS study of the Eu{sub 1.92}Fe{sub 0.08}O{sub 3} film shows that Fe exists in Fe{sup 3+} ionic state in the film. The film exhibits magnetic ordering at room temperature.

  9. Cell wall composition of Bacillus subtilis changes as a function of pH and Zn²⁺ exposure: insights from cryo-XPS measurements.

    PubMed

    Ramstedt, Madeleine; Leone, Laura; Persson, Per; Shchukarev, Andrey

    2014-04-22

    Bacteria play an important role in the biogeochemical cycling of metals in the environment. Consequently, there is an interest to understand how the bacterial surfaces interact with metals in solution and how this affects the bacterial surface. In this work we have used a surface-sensitive analysis technique, cryogenic X-ray photoelectron spectroscopy (cryo-XPS), to monitor the surface of Bacillus subtilis cells as a function of pH and Zn(2+) content in saline solution. The objective of the study was twofold: (1) to investigate the agreement between two data treatment methods for XPS, as well as investigate to what extent sample pretreatment may influence XPS data of bacterial samples, and (2) to characterize how the surface chemistry of bacterial cells is influenced by different external conditions. (1) It was found that the two data treatment methods gave rise to comparable results. However, identical samples analyzed fast-frozen or dry exhibited larger differences in surface chemistry, indicating that sample pretreatment can to large extents influence the obtained surface composition of bacterial samples. (2) The bacterial cell wall (in fast-frozen samples) undergoes dramatic compositional changes with pH and with Zn(2+) exposure. The compositional changes are interpreted as an adaptive metal resistance response changing the biochemical composition of the bacterial cell wall. These results have implications for how adsorption processes at the surface of bacterial cells are analyzed, understood, modeled, and predicted.

  10. TAT peptide immobilization on gold surfaces: a comparison study with a thiolated peptide and alkylthiols using AFM, XPS, and FT-IRRAS.

    PubMed

    Cho, Youngnam; Ivanisevic, Albena

    2005-04-01

    A TAT peptide was used to functionalize a gold surface by three different methods: adsorption from solution, microcontact printing, and dip-pen nanolithography (DPN). The composition and structure of the modified gold was characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and Fourier transform -infrared reflection absorption spectroscopy (FT-IRRAS). We used two well-studied alkylthiols, mercaptohexadecanoic acid and 1-octadecanethiol, as a comparison in order to understand the structure of the TAT peptide monolayers prepared by the three methods. AFM studies allowed us to assess the homogeneity after each modification protocol. XPS was used to characterize the chemical composition of the gold surface after each functionalization procedure. The XPS results showed that surfaces modified with the TAT peptide by the three methods exhibit similar surface chemistry. Finally, FT-IRRAS experiments allowed us to conclude that the structure of the alkyl chains of the TAT peptides is fairly disordered and different after each procedure. Regardless of the type of surface functionalization method used, the monolayer of TAT peptide formed on the surface was of "liquidlike" nature.

  11. XPS studies of Pt catalysts supported on porous carbon

    NASA Astrophysics Data System (ADS)

    Tyagi, Deepak; Varma, Salil; Bharadwaj, S. R.

    2016-05-01

    Pt catalysts supported on porous carbon were prepared by hard templating route and used for HI decomposition reaction of Sulfur Iodine thermochemical cycle. These catalysts were characterized by X-ray photoelectron spectroscopy for oxidation state of platinum as well as nature of carbon present in the catalysts. It was found that platinum is present in metallic state and carbon is present in both sp2 and sp3 hybridization states. The catalysts were evaluated for their activity and stability for liquid phase HI decomposition reaction and it was observed that mesoporous carbon based catalysts were more active and stable under the reaction conditions.

  12. An X-ray photoelectron spectroscopic study of the B-N-Ti system

    SciTech Connect

    Seal, S.; Barr, T.L.; Sobczak, N.; Benko, E.; Morgiel, J.

    1997-03-01

    Composite nitrides (such as BN, TiN) are widely used in various industrial applications because of their extreme wear and corrosion resistance, thermal and electrical properties. In order to obtain composite materials with these optimal properties, it is important to elucidate whether any chemical reactions occur at nitride/metal interfaces, e.g., those involving BN-Ti/TiN. Materials of interest include the deposition by PVD of Ti and TiN on BN substrates. Some of these systems were then subjected to varying degrees of physical and thermal alteration. Detailed X-ray photoelectron spectroscopy (XPS) has therefore been rendered of these interfaces using cross-sectional display and sputter etching. Resulting structural and morphological features have been investigated with transmission electron microscopy (TEM) and X-ray diffraction (XRD). Diffusion of the nitridation, oxynitride formation and interfacial growth are of general interest.

  13. Surface state analysis of wet ground silicon nitride powders by x-ray photoelectron spectroscopy

    SciTech Connect

    Kameshima, Yoshikazu; Yasumori, Atsuo; Okada, Kiyoshi

    1995-09-01

    Three kinds of silicon nitride powders, i.e. as-prepared direct-nitridation powder, HF-treated direct-nitridation powder, and as-prepared imide decomposition powder, were wet ground by ball milling in water and the surface state change due to the grinding was examined by X-ray photoelectron spectroscopy (XPS) and X-ray Auger electron spectroscopy (XAES). The thickness of the oxidized surface layer of the powder was calculated from the peak area ratio and the chemical composition was evaluated from the Auger parameter (AP). Surface oxidized phase amount gradually increased with longer milling time and the thickness increased almost three times after 7 days milling, compared to as those of the unground samples. Chemical composition of the oxidized phase formed by the grinding was pure silica irrespective to the samples, although those of the oxidized phase in the unground samples differed among the samples.

  14. Uses of Auger and x ray photoelectron spectroscopy in the study of adhesion and friction

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa

    1990-01-01

    Three studies are described characterizing the possible contributions of surface science to tribology. These include surface contamination formed by the interaction of a surface with the environment, contaminants obtained with diffusion of compounds, and surface chemical changes resulting from selective thermal evaporation. Surface analytical tools such as Auger electron spectroscopy (AES) and x ray photoelectron spectroscopy (XPS) incorporated directly into adhesion and friction systems are primarily used to define the nature of tribological surfaces before and after tribological experimentation and to characterize the mechanism of solid-to-solid interaction. Emphasis is on fundamental studies involving the role of surfaces in controlling the adhesion and friction properties of materials emerging as a result of the surface analyses. The materials which were studied include metals and ceramics such as elemental metals, amorphous alloys (metallic glasses), and silicon-based ceramics.

  15. Effect of X-ray flux on polytetrafluoroethylene in X-ray photoelectron spectroscopy

    NASA Technical Reports Server (NTRS)

    Wheeler, D. R.; Pepper, S. V.

    1982-01-01

    The effect of the X-ray flux in X-ray photoelectron spectroscopy (STAT) on the constitution of the polytetrafluoroethylene (PTFE) surface has been examined. The radiation dose rate for our specimen was about 10 to the 7th rad/s. The structure, magnitude and binding energy of the C(1s) and F(1s) features of the XPS spectrum and the mass spectrum of gaseous species evolved during irradiation are observed. The strong time dependence of these signals over a period of several hours indicated that the surface constitution of PTFE is greatly affected by this level of radiation dose. The results are consistent with the development of a heavily cross-linked or branched structure in the PTFE surface region and the evolution of short chain fragments into the gas phase.

  16. High-resolution pulsed-field ionization photoelectron spectroscopy using multi-bunch synchrotron radiation

    SciTech Connect

    Hsu, C.W.; Evans, M.; Ng, C.Y.; Heimann, P.

    1997-04-01

    BL9.0.2.2 is the newly constructed experimental End Station 2 at the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source (ALS). It is dedicated to the high resolution photoionization study of molecules of interest to atmospheric and combustion chemistry. This End Station is equipped with a high resolution scanning monochromator, which has been demonstrated to have a world record resolution of E/{delta}E=70,000. Taking the advantage of the high resolution ALS light, the authors have improved the energy resolution in threshold photoelectron spectroscopy (TPES) to 0.8 meV. The TPES is a popular technique for photoionization experiments at all synchrotron radiation facilities due to its high energy resolution as compared to that of traditional photoelectron spectroscopy (PES). TPES achieves higher energy resolution by preferentially detecting near zero kinetic energy photoelectrons resulting from threshold photoionization. However, the spectra obtained from the TPES technique generally are complicated by the simultaneous detection of electrons with nonzero kinetic energy, which are not fully discriminated against. On the other hand, the spectra obtained from pulsed field ionization photoelectron spectroscopy (PFI-PES) are completely free of the contamination from kinetic electrons. The PFI-PE technique basically involves the detection of the photoelectrons from field ionization of the very high-n Rydberg states, a few cm{sup {minus}1} below the ionization energy (IE), by applying a delayed pulsed electric field. Within a delay of a few microseconds, all the prompt electrons formed from direct ionization will escape from the photoionization region and will not be collected. The authors have recently overcome problems with energy resolution of an electron time-of-flight technique, and incorporated the PFI-PE technique with multi-bunch VUV synchrotron radiation.

  17. Acid—base behavior of aluminum and silicon oxides — a combination of two approaches: XPS and Lewis acido-basicity; rest potential and Brönsted acido-basicity

    NASA Astrophysics Data System (ADS)

    Casamassima, M.; Darque-Ceretti, E.; Etcheberry, A.; Aucouturier, M.

    1991-11-01

    In the frame of an investigation on adhesion phenomena between elastomers and oxide substrates, X-ray photoelectron spectroscopy (XPS) and rest electrochemical potential measurements have been used in order to attempt a characterization of the reactivity of various oxides. The first step of the study is a definition of donor/acceptor properties for a solid surface in an interactive model such as the Lewis one. In this case, the Fermi level is an appropriate parameter. An experimental approach is developed to estimate this parameter through photoelectronical data obtained by XPS. As proposed by Mullins and Averbach in 1988 in the case of Al and Si oxides, XPS allows an estimation of the Fermi energy EF, defined as the energy difference between the Fermi level and the upper occupied valence band. A classification of EF values is obtained for different samples of aluminum and silicon oxides; the donor (acceptor) behavior increases for decreasing (increasing) EF. The second step is the validation of the EF classification obtained by XPS. A potentiometric method is used to estimate the rest potential Eo in aqueous solution. The relationship between the Eo and the solution pH is a Nernst law for a large range of pH values, which means that the system is governed by acid-base interactions in Brönsted definition in the interfacial area. When the nature of the oxide substrate is modified, the translation of the Eo versus pH line can be correlated with the EF classification obtained previously. This confirms the relationship already reported between point of zero charge and EF. It can also be considered as a validation of the idea that XPS allows the classification of EF values for those oxides.

  18. Electronic structure and optical properties of Cs2HgCl4: DFT calculations and X-ray photoelectron spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Parasyuk, O. V.; Fedorchuk, A. O.; Khyzhun, O. Y.

    2016-10-01

    A high-quality single crystal of cesium mercury tetrabromide, Cs2HgCl4, was synthesized by using the vertical Bridgman-Stockbarger method and its electronic structure was studied from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectra were measured for both pristine and Ar+ ion-bombarded Cs2HgCl4 single crystal surfaces. The present XPS measurements indicate that the Cs2HgCl4 single crystal surface is sensitive with respect to Ar+ ion-bombardment: such a treatment changes substantially its elemental stoichiometry. With the aim of exploring total and partial densities of states within the valence band and conduction band regions of the Cs2HgCl4 compound, band-structure calculations based on density functional theory (DFT) using the augmented plane wave + local orbitals (APW + lo) method as incorporated within the WIEN2k package are performed. The calculations indicate that the Cl 3p states are the principal contributors in the upper portion of the valence band, while the Hg 5d and Cs 5p states dominate in its lower portion. In addition, the calculations allow for concluding that the unoccupied Cl p and Hg s states are the main contributors to the bottom of the conduction band. Furthermore, main optical characteristics of Cs2HgCl4, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity, are elucidated based on the DFT calculations.

  19. X-ray photoelectron spectroscopy study of high-k CeO{sub 2}/La{sub 2}O{sub 3} stacked dielectrics

    SciTech Connect

    Zhang, Jieqiong; Wong, Hei; Yu, Danqun; Kakushima, Kuniyuki; Iwai, Hiroshi

    2014-11-15

    This work presents a detailed study on the chemical composition and bond structures of CeO{sub 2}/La{sub 2}O{sub 3} stacked gate dielectrics based on x-ray photoelectron spectroscopy (XPS) measurements at different depths. The chemical bonding structures in the interfacial layers were revealed by Gaussian decompositions of Ce 3d, La 3d, Si 2s, and O 1s photoemission spectra at different depths. We found that La atoms can diffuse into the CeO{sub 2} layer and a cerium-lanthanum complex oxide was formed in between the CeO{sub 2} and La{sub 2}O{sub 3} films. Ce{sup 3+} and Ce{sup 4+} states always coexist in the as-deposited CeO{sub 2} film. Quantitative analyses were also conducted. The amount of CeO{sub 2} phase decreases by about 8% as approaching the CeO{sub 2}/La{sub 2}O{sub 3} interface. In addition, as compared with the single layer La{sub 2}O{sub 3} sample, the CeO{sub 2}/La{sub 2}O{sub 3} stack exhibits a larger extent of silicon oxidation at the La{sub 2}O{sub 3}/Si interface. For the CeO{sub 2}/La{sub 2}O{sub 3} gate stack, the out-diffused lanthanum atoms can promote the reduction of CeO{sub 2} which produce more atomic oxygen. This result confirms the significant improvement of electrical properties of CeO{sub 2}/La{sub 2}O{sub 3} gated devices as the excess oxygen would help to reduce the oxygen vacancies in the film and would suppress the formation of interfacial La-silicide also.

  20. Photoelectron Quantum Yields of the Amino Acids

    PubMed Central

    Dam, Rudy J.; Burke, Charles A.; Griffith, O. Hayes

    1974-01-01

    The photoelectron quantum yields of 21 common amino acids and 15 polyamino acids were measured in the 180-240 nm wavelength region. On the average, the quantum yields of these two groups exhibit quite similar wavelength dependence. For λ > 220 nm all amino acid and polyamino acid quantum yields are ≤10-7 electrons/(incident) photon. The mean yields increase to about 5 × 10-7 electrons/photon at 200 nm and 5 × 10-6 electrons/photon at 180 nm. L-tryptophan, L-tyrosine, and poly-L-tryptophan exhibit above average yields between 180 and 200 nm. Comparison with the dye phthalocyanine indicates that the quantum yield of the dye is two orders of magnitude greater than that of the amino acids from 200 to 240 nm, suggesting the feasibility of photoelectron labeling studies of biological surfaces. PMID:4836100

  1. Theory of photoelectron production, transport and energy loss

    NASA Technical Reports Server (NTRS)

    Nagy, A. F.

    1974-01-01

    Current understanding of the theory of ionospheric photoelectron production, transport and energy loss is summarized. The various approaches used in the theoretical calculations of photoelectron fluxes appear to be self consistent and sound; improved values for a number of input parameters are needed now in order to achieve significant improvements and more confidence in the results. The major remaining problem in the present day theory of photoelectron transport and energy loss is centered around the calculations of photoelectron transit through the protonosphere.

  2. Chemical state analysis of trace-level alkali metals sorbed in micaceous oxide by total reflection X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Baba, Y.; Shimoyama, I.; Hirao, N.

    2016-10-01

    In order to determine the chemical states of radioactive cesium (137Cs or 134Cs) sorbed in clay minerals, chemical states of cesium as well as the other alkali metals (sodium and rubidium) sorbed in micaceous oxides have been investigated by X-ray photoelectron spectroscopy (XPS). Since the number of atoms in radioactive cesium is extremely small, we specially focused on chemical states of trace-level alkali metals. For this purpose, we have measured XPS under X-ray total reflection (TR) condition. For cesium, it was shown that ultra-trace amount of cesium down to about 100 pg cm-2 can be detected by TR-XPS. This amount corresponds to about 200 Bq of 137Cs (t1/2 = 30.2 y). It was demonstrated that ultra-trace amount of cesium corresponding to radioactive cesium level can be measured by TR-XPS. As to the chemical states, it was found that core-level binding energy in TR-XPS for trace-level cesium shifted to lower-energy side compared with that for thicker layer. A reverse tendency is observed in sodium. Based on charge transfer within a simple point-charge model, it is concluded that chemical bond between alkali metal and micaceous oxide for ultra-thin layer is more polarized that for thick layer.

  3. X-ray photoelectron spectroscopy, depth profiling, and elemental imaging of metal/polyimide interfaces of high density interconnect packages subjected to temperature and humidity

    SciTech Connect

    Jung, David R.; Ibidunni, Bola; Ashraf, Muhammad

    1998-11-24

    X-ray photoelectron spectroscopy (XPS) was used to analyze surfaces and buried interfaces of a tape ball grid array (TBGA) interconnect package that was exposed to temperature and humidity testing (the pressure cooker test or PCT). Two metallization structures, employing 3.5 and 7.5 nm Cr adhesion layers, respectively, showed dramatically different results in the PCT. For the metallization with 3.5 nm Cr, spontaneous failure occurred on the polymer side of the metal/polyimide interface. Copper and other metals were detected by XPS on and below this polymer surface. For the metallization with 7.5 nm Cr, which did not delaminate in the PCT, the metallization was manually peeled away and also showed failure at the polymer side of the interface. Conventional XPS taken from a 1 mm diameter area showed the presence of metals on and below this polymer surface. Detailed spatially-resolved analysis using small area XPS (0.1 mm diameter area) and imaging XPS (7 {mu}m resolution) showed that this metal did not migrate through and below the metal/polymer interface, but around and outside of the metallized area.

  4. Secondary electron measurement and XPS characterization of NEG coatings

    SciTech Connect

    Sharma, R. K. Sinha, Atul K. Gupta, Nidhi Nuwad, J. Jagannath, Gadkari, S. C. Singh, M. R. Gupta, S. K.

    2014-04-24

    Ternary alloy coatings of IVB and VB materials provide many of benefits over traditional material surfaces such as creation of extreme high vacuum(XHV), lower secondary electron yield(SEY), low photon desorption coefficient. XHV (pressure < 10{sup −10} mbar) is very useful to the study of surfaces of the material in as it is form, high energy particle accelerators(LHC, Photon Factories), synchrotrons (ESRF, Ellectra) etc.. Low secondary electron yield leads to very low multi-pacting utilizes to increase beam life time. In this paper preparation of the coatings and a study of secondary electron yield measurement after heating at different temperatures has been shown also results of their surface characterization based on shift in binding energy has been produced using the surface techniques XPS. Stoichiometry of the film was measured by Energy dispersive x-ray analysis (EDX)

  5. XPS Study of Counterion Incorporation into Poly(vinylferrocene).

    PubMed

    Zeng, X; Moon, S; Bruckenstein, S; Hillman, A R

    1998-07-01

    XPS provides answers to two significant issues that arise in studying electroactive polymers. First, what fraction of possible charge centers participates in the redox process? Second, what are the relative partition coefficients of two counterions that compete as charge-compensating counterions? To answer both these questions, we emersed (or immersed) poly(vinylferrocene) films from (or into) supporting electrolytes while maintaining potential control to govern the electrochemical history of the electroactive film. We found that all ferrocene units in the surface of a poly(vinylferrocene) film deposited on gold can be oxidized when the counterion is perchlorate, tetrafluoroborate, hexafluorophosphate, tosylate, or 1,5-naphthalenedisulfonate. In answering the second question, no internal standard was needed:  the concentration ratios of the two competing ions in both water and polymer phases were used as the experimental variables. For the completely oxidized ferricinium film, we found that the partition coefficient of perchlorate ions is 67% of that of fluoroborate ions.

  6. Probing neutral atmospheric collision complexes with anion photoelectron imaging

    NASA Astrophysics Data System (ADS)

    Jarrold, Caroline

    Photodetachment of anionic precursors of neutral collision complexes offers a way to probe the effects of symmetry-breaking collision events on the electronic structure of normally transparent molecules. We have measured the anion photoelectron imaging (PEI) spectra of a series of O2- X complexes, where X is a volatile organic molecule with atmospheric relevance, to determine how the electronic properties of various X molecules affect the low-lying electronic structure of neutral O2 undergoing O2 - X collisons. The study was motivated by the catalog of vibrational and electronic absorption lines induced by O2 - O2, O2 - N2, and other collisions. The energies of electronic features observed in the anion PEI spectra of O2- X (X = hexane, hexene, isoprene and benzene) relative to O2- PEI spectroscopic features indicate that photodetachment of the anion does indeed access a repulsive part of the O2 - X potential. In addition, the spectra of the various complexes show an interesting variation in the intensities of transitions to the excited O2(1Δg) . X and O2(1Σg+) . X states relative to the ground O2(3Σg-) . X state. With X = non-polar species such as hexane, the relative intensities of transitions to the triplet and singlet states of O2 . X are very similar to those of isolated O2, while the relative intensity of the singlet band decreases and becomes lower in energy relative to the triplet band for X = polar molecules. A significant enhancement in the intensities of the singlet bands is observed for complexes with X = isoprene and benzene, both of which have low-lying triplet states. The role of the triplet states in isoprene and benzene, and the implications for induced electronic absorption in O2 undergoing collisions with these molecules, are explored. National Science Foundation NSF CHE 1265991.

  7. Os layers spontaneously deposited on the Pt(111) electrode : XPS, STM and GIF-XAS study.

    SciTech Connect

    Rhee, C. K.; Wakisaka, M.; Tolmachev, Y.; Johnston, C.; Haasch, R.; Attenkofer, K.; Lu, G. Q.; You, H.; Wieckowski, A.; Univ. of Illinois Champaigh-Urbana

    2003-01-01

    expected from voltammetry. Also, the observed intensity of the white line of Os in the 100-400 mV region is larger than the value reported for metallic bulk Os. This discrepancy may result from the difference in the electronic properties of the metallic Os layers on Pt(111) and the metallic bulk Os: in the potential region between 100 and 400 mV, the 5d electrons in Os and Pt form a mixed electronic band, and the density of electronic states near the Fermi level, the main factor determining the white line intensity, may not be the same as in metallic bulk. The presented results on osmium adlayers are much more comprehensive than those available in our previous work due to the combined STM, GIF-XAS and XPS investigations. A nearly perfect convergence of the in situ and ex situ data is one of the main research outcomes of this project. Finally, platinum XPS spectra taken in the context of Os electrooxidation from the electrode surface are also presented and conclusions are made, that up to 900 mV platinum remain metallic, irrespective of a significant osmium oxidation on its surface.

  8. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    SciTech Connect

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOH and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  9. Closing the pressure gap in x-ray photoelectron spectroscopy by membrane hydrogenation

    SciTech Connect

    Delmelle, Renaud; Borgschulte, Andreas; Probst, Benjamin; Alberto, Roger; Züttel, Andreas; Bleiner, Davide

    2015-05-15

    Comprehensive studies of gas-solid reactions require the in-situ interaction of the gas at a pressure beyond the operating pressure of ultrahigh vacuum (UHV) X-ray photoelectron spectroscopy (XPS). The recent progress of near ambient pressure XPS allows to dose gases to the sample up to a pressure of 20 mbar. The present work describes an alternative to this experimental challenge, with a focus on H{sub 2} as the interacting gas. Instead of exposing the sample under investigation to gaseous hydrogen, the sample is in contact with a hydrogen permeation membrane, through which hydrogen is transported from the outside to the sample as atomic hydrogen. Thereby, we can reach local hydrogen concentrations at the sample inside an UHV chamber, which is equipped with surface science tools, and this corresponds to a hydrogen pressure up to 1 bar without affecting the sensitivity or energy resolution of the spectrometer. This experimental approach is validated by two examples, that is, the reduction of a catalyst precursor for CO{sub 2} hydrogenation and the hydrogenation of a water reduction catalyst for photocatalytic H{sub 2} production, but it opens the possibility of the new in situ characterisation of energy materials and catalysts.

  10. Internal Photoemission and X-Ray Photoelectron Spectroscopic Studies of Sulfur-Passivated GaAs

    NASA Astrophysics Data System (ADS)

    Sato, Kenji; Ikoma, Hideaki

    1993-02-01

    Internal photoemission and X-ray photoelectron spectroscopic (XPS) measurements were performed to investigate the effect of sulfur passivation on the GaAs surface and the degradation of the GaAs surface exposed to air ambient after the passivation. The reverse bias dependence of the Schottky barrier height was very small in the as-sulfur-treated sample and was mainly explained by the image force lowering effect. However, it increased as this sample was exposed to air, indicating an increase in the interface state density. The XPS studies showed that both the Ga and As oxides were hardly observed in the sulfur-passivated samples. This indicates that sulfur passivation strongly suppresses oxidation of GaAs. However, a small amount of elemental arsenic was observed with a trace of the As suboxides (such as AsO) after exposure to air and it increased as the exposure time was increased. These results were probably correlated with the increase in the bias dependence of the Schottky barrier height in samples exposed to air after the passivation. Thermal oxidation of GaAs was found to be retarded by sulfur passivation until oxidation time was about 10 min at 300°C. A possible model of suppression of oxidation by sulfur passivation was also discussed.

  11. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    DOE PAGES

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOHmore » and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.« less

  12. Study of the oxidation of gold-tin preforms using x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Taylor, J. Ashley; Merchant, Sailesh M.; Perry, D. L.

    1995-11-01

    This study uses x-ray photoelectron spectroscopy (XPS) to investigate the nature of the oxide formed on clean Au-Sn binary alloys (ζ and δ phases) and on preforms with the eutectic composition (29 at % Sn) at low O2 pressures (<10-3 Torr) and at high O2 pressures (up to one atmosphere) at temperatures ranging from room temperature to 200 °C. Sn Auger parameters and XPS angular-resolved data were obtained in addition to the core binding energies to identify the oxide layer. The oxidation of the Au-Sn alloys is basically similar to the oxidation of metallic Sn. The Auger parameter indicates that with low-pressure oxidation a layered oxide structure is formed consisting of SnO and a slightly tin-rich oxide at the interface. Probably a thin skin of Sn(IV) oxide exists on the outer surface of the low-pressure oxide. High-temperature and low-pressure promotes the growth of SnO. As the pressure is increased the Sn(IV) oxide grows more noticeably and with high-pressure oxidation the Sn(IV) oxide grows thicker than the Sn(II) oxide at the interface. The Sn(II) oxide at the interface appears similar to the Sn(II) oxide structure formed at low pressure. The Auger parameter indicates that the Sn(IV) oxide possesses a structure different than that of Cassiterite.

  13. Closing the pressure gap in x-ray photoelectron spectroscopy by membrane hydrogenation

    NASA Astrophysics Data System (ADS)

    Delmelle, Renaud; Probst, Benjamin; Alberto, Roger; Züttel, Andreas; Bleiner, Davide; Borgschulte, Andreas

    2015-05-01

    Comprehensive studies of gas-solid reactions require the in-situ interaction of the gas at a pressure beyond the operating pressure of ultrahigh vacuum (UHV) X-ray photoelectron spectroscopy (XPS). The recent progress of near ambient pressure XPS allows to dose gases to the sample up to a pressure of 20 mbar. The present work describes an alternative to this experimental challenge, with a focus on H2 as the interacting gas. Instead of exposing the sample under investigation to gaseous hydrogen, the sample is in contact with a hydrogen permeation membrane, through which hydrogen is transported from the outside to the sample as atomic hydrogen. Thereby, we can reach local hydrogen concentrations at the sample inside an UHV chamber, which is equipped with surface science tools, and this corresponds to a hydrogen pressure up to 1 bar without affecting the sensitivity or energy resolution of the spectrometer. This experimental approach is validated by two examples, that is, the reduction of a catalyst precursor for CO2 hydrogenation and the hydrogenation of a water reduction catalyst for photocatalytic H2 production, but it opens the possibility of the new in situ characterisation of energy materials and catalysts.

  14. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2016-01-01

    In this work, a detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented for select MXenes-a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Herein we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, sbnd O, sbnd OH and sbnd F, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. From XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  15. Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

    NASA Astrophysics Data System (ADS)

    Lehmann, C. Stefan; Ram, N. Bhargava; Powis, Ivan; Janssen, Maurice H. M.

    2013-12-01

    Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

  16. Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

    SciTech Connect

    Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M.; Powis, Ivan

    2013-12-21

    Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

  17. X-Ray Photoelectron Spectroscopic Analysis of the Oxide of GaAs

    NASA Astrophysics Data System (ADS)

    Ishikawa, Toshifumi; Ikoma, Hideaki

    1992-12-01

    Oxides of GaAs grown using various oxidation processes were analyzed with X-ray photoelectron spectroscopy (XPS). Oxides investigated were the native (naturally grown or exposed to air), the chemical (grown in boiling deionized water) and the thermal (at 350°C and 500°C in dry oxygen) ones. With the use of a spectral deconvolution technique, all types of suboxides of both As and Ga including elemental arsenic were observed in addition to well-known As2O3 and Ga2O3. Elemental arsenic is considered to be one of the oxidized forms of GaAs. As2O5 was observed in the thermal oxides. In the chemical oxide and the native oxide grown in short exposure to air, elemental arsenic is the main component of oxide, while As2O3 is the dominant species in more highly oxidized films such as the thermal oxide. XPS data suggest that oxidation of As bonded in GaAs proceeds as GaAs→elemental As (As0)→As2O (As1+)→AsO (As2+)→As2O3 (As3+)→As2O5 (As5+). Oxidation of Ga bonded in GaAs advances as GaAs→Ga2O (Ga1+)→GaO (Ga2+)→Ga2O3 (Ga3+). Angle-resolved XPS measurements and semiquantitative analyses of these data were performed and an effective thickness of each oxide was also derived with simplified assumptions. The native and the chemical oxides were nearly stoichiometric. However, the thermal oxide was substantially Ga-rich due to desorption and evaporation of As2O3 from the surface during oxidation.

  18. Tracking the conversion of nitrogen during pyrolysis of antibiotic mycelial fermentation residues using XPS and TG-FTIR-MS technology.

    PubMed

    Zhu, Xiangdong; Yang, Shijun; Wang, Liang; Liu, Yuchen; Qian, Feng; Yao, Wenqing; Zhang, Shicheng; Chen, Jianmin

    2016-04-01

    Antibiotic mycelial fermentation residues (AMFRs), which are emerging solid pollutants, have been recognized as hazardous waste in China since 2008. Nitrogen (N), which is an environmental sensitivity element, is largely retained in AMFR samples derived from fermentation substrates. Pyrolysis is a promising technology for the treatment of solid waste. However, the outcomes of N element during the pyrolysis of AMFRs are still unknown. In this study, the conversion of N element during the pyrolysis of AMFRs was tracked using XPS (X-ray photoelectron spectroscopy) and online TG-FTIR-MS (Thermogravimetry-Fourier transform infrared-Mass spectrometry) technology. In the AMFR sample, organic amine-N, pyrrolic-N, protein-N, pyridinic-N, was the main N-containing species. XPS results indicated that pyrrolic-N and pyridinic-N were retained in the AMFR-derived pyrolysis char. More stable species, such as N-oxide and quaternary-N, were also produced in the char. TG-FTIR-MS results indicated that NH3 and HCN were the main gaseous species, and their contents were closely related to the contents of amine-N and protein-N, and pyrrolic-N and pyridinic-N of AMFRs, respectively. Increases in heating rate enhanced the amounts of NH3 and HCN, but had less of an effect on the degradation degree of AMFRs. N-containing organic compounds, including amine-N, nitrile-N and heterocyclic-N, were discerned from the AMFR pyrolysis process. Their release range was extended with increasing of heating rate and carbon content of AMFR sample. This work will help to take appropriate measure to reduce secondary pollution from the treatment of AMFRs.

  19. Adenine adlayers on Cu(111): XPS and NEXAFS study

    SciTech Connect

    Tsud, Nataliya; Bercha, Sofiia; Ševčíková, Klára; Matolín, Vladimír; Acres, Robert G.; Prince, Kevin C.

    2015-11-07

    The adsorption of adenine on Cu(111) was studied by photoelectron and near edge x-ray absorption fine structure spectroscopy. Disordered molecular films were deposited by means of physical vapor deposition on the substrate at room temperature. Adenine chemisorbs on the Cu(111) surface with strong rehybridization of the molecular orbitals and the Cu 3d states. Annealing at 150 °C caused the desorption of weakly bonded molecules accompanied by formation of a short-range ordered molecular adlayer. The interface is characterized by the formation of new states in the valence band at 1.5, 7, and 9 eV. The present work complements and refines existing knowledge of adenine interaction with this surface. The coverage is not the main parameter that defines the adenine geometry and adsorption properties on Cu(111). Excess thermal energy can further rearrange the molecular adlayer and, independent of the initial coverage, the flat lying stable molecular adlayer is formed.

  20. High-resolution threshold photoelectron study of the propargyl radical by the vacuum ultraviolet laser velocity-map imaging method

    NASA Astrophysics Data System (ADS)

    Gao, Hong; Xu, Yuntao; Yang, Lei; Lam, Chow-Shing; Wang, Hailing; Zhou, Jingang; Ng, C. Y.

    2011-12-01

    By employing the vacuum ultraviolet (VUV) laser velocity-map imaging (VMI) photoelectron scheme to discriminate energetic photoelectrons, we have measured the VUV-VMI-threshold photoelectrons (VUV-VMI-TPE) spectra of propargyl radical [C3H3({tilde X}{}^2B_1)] near its ionization threshold at photoelectron energy bandwidths of 3 and 7 cm-1 (full-width at half-maximum, FWHM). The simulation of the VUV-VMI-TPE spectra thus obtained, along with the Stark shift correction, has allowed the determination of a precise value 70 156 ± 4 cm-1 (8.6982 ± 0.0005 eV) for the ionization energy (IE) of C3H3. In the present VMI-TPE experiment, the Stark shift correction is determined by comparing the VUV-VMI-TPE and VUV laser pulsed field ionization-photoelectron (VUV-PFI-PE) spectra for the origin band of the photoelectron spectrum of the {tilde X}^ + {- tilde X} transition of chlorobenzene. The fact that the FWHMs for this origin band observed using the VUV-VMI-TPE and VUV-PFI-PE methods are nearly the same indicates that the energy resolutions achieved in the VUV-VMI-TPE and VUV-PFI-PE measurements are comparable. The IE(C3H3) value obtained based on the VUV-VMI-TPE measurement is consistent with the value determined by the VUV laser PIE spectrum of supersonically cooled C3H3({tilde X}{}^2B_1) radicals, which is also reported in this article.

  1. A Multi-technique Characterization of Adsorbed Protein Films: Orientation and Structure by ToF-SIMS, NEXAFS, SFG, and XPS

    NASA Astrophysics Data System (ADS)

    Baio, Joseph E.

    There are many techniques that allow surface scientists to study interfaces. However, few are routinely applied to probe biological surfaces. The work presented here demonstrates how detailed information about the conformation, orientation, chemical state, and molecular structure of biological molecules immobilized onto a surface can be assessed by electron spectroscopy, mass spectrometry, and nonlinear vibrational spectroscopy techniques. This investigation began with the development of simple model systems (small proteins, and peptides) and evolved into a study of more complex --- real world systems. Initially, two model systems based on the chemical and electrostatic immobilization of a small rigid protein (Protein G B1 domain, 6kDa) were built to develop the capabilities of time-of-flight secondary ion mass spectrometry (ToFSIMS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and sum frequency generation (SFG) spectroscopy as tools to probe the structure of surface immobilized proteins. X-ray photoelectron spectroscopy (XPS) was used to measure the amount of immobilized protein and ToF-SIMS sampled the amino acid composition of the exposed surface of the protein film. Within the ToF-SIMS spectra, an enrichment of secondary ions from amino acids located at opposite ends of the proteins were used to describe protein orientation. SFG spectral peaks characteristic of ordered alpha-helix and beta-sheet elements were observed for both systems and the phase of the peaks indicated a predominantly upright orientation for both the covalent and electrostatic configurations. Polarization dependence of the NEXAFS signal from the N 1s to pi* transition of the peptide bonds that make up the beta-sheets also indicated protein ordering at the surface. Building upon the Protein G B1 studies, the orientation and structure of a surface immobilized antibody (HuLys Fv: variant of humanized anti-lysozyme variable fragment, 26kDa) was characterized across two

  2. X-ray photoelectron spectroscopic evidence for bacteria-enhanced dissolution of hornblende

    NASA Astrophysics Data System (ADS)

    Kalinowski, B. E.; Liermann, L. J.; Brantley, S. L.; Barnes, A.; Pantano, C. G.

    2000-04-01

    An Arthrobacter species capable of extracting Fe from hornblende was isolated from a soil from the Adirondacks, NY (USA). This bacteria isolate, used in batch experiments with hornblende, accelerated the release of Fe from hornblende without measurably affecting Al release. The isolate produces both low molecular weight organic acids (LMWOA) and a catecholate siderophore. Polished hornblende (glass and crystal) discs were analyzed with X-ray photoelectron spectroscopy (XPS) before and after incubation with growing Arthrobacter sp. to investigate whether the bacteria caused a distinguishable chemical signature on the upper 100 Å of mineral surface. After removal of the arthrobacter grown on hornblende crystal or glass substrates using lysozyme, XPS revealed surface depletion of Fe for samples grown for several days in buffered (crystal) and unbuffered (crystal and glass) media. Fe/Si ratios of hornblende surfaces dissolved under biotic conditions are significantly lower than Fe/Si ratios on surfaces dissolved under abiotic conditions for similar amounts of time. Enhanced Fe release and the formation of Fe-depleted surfaces is inferred to be caused by catechol complexation at the mineral surface. Because natural siderophore was not isolated in sufficient quantities to run bacteria-free leaching experiments, parallel investigations were run with a commercially available siderophore (desferrioxamine B). Desferrioxamine B was observed to enhance release of Fe, Si, and Al from hornblende both with and without added bacteria. Formation of desferrioxamine-Fe surface complexes were probed by studying the multiple splitting and shift in intensities of the N 1s line analyzed by XPS on siderophore ± Fe on gold surfaces and siderophore + hornblende crystal surfaces. Based upon the observed formation of an hydroxamate (desferrioxamine) surface complex on hornblende, we infer that catecholate siderophores, such as those produced by the arthrobacter, also complex on the

  3. Analyse de l'interface cuivre/Teflon AF1600 par spectroscopie des photoelectrons rayons x

    NASA Astrophysics Data System (ADS)

    Popovici, Dan

    The speed of electrical signals through the microelectronic multilevel interconnects depends of the delay time R x C. In order to improve the transmission speed of future microdevices, the microelectronics industry requires the use of metals having lower resistivities and insulators having lower permittivities. Copper and fluoropolymers are interesting candidates for the replacement of the presently used Al/polyimide technology. This thesis presents an X-ray photoelectron spectroscopy (XPS) analysis of the Cu/Teflon AF1600 interface, in order to have a better understanding of those interfacial interactions leading to improved adhesion. Several deposition methods, such as evaporation, sputtering and laser-induced chemical deposition were analyzed and compared. X-ray photoelectron spectroscopy (XPS) was used as the primary characterization technique of the different surfaces and interfaces. In the case of evaporation and sputtering, the loss of fluorine and oxygen atoms leads to graphitization and the crosslinking of carbon chains. The extent of damage caused by copper deposition is higher for sputter deposition because of the higher energies of the incidents atoms. This energy (two orders of magnitude higher than the energy involved in the evaporation) is also responsible for the total reaction of Cu with F and C. For the physical depositions (sputtering and evaporation), an angle-resolved XPS diffusion study showed the copper distribution as a function of depth. (i) For sputter deposition, this distribution is uniform. (ii) In the case of evaporation, we computed the concentration profile using the inverse Laplace transform. Several samples, annealed at different temperatures, were used to calculate the diffusion coefficients for the Cu/Teflon AF1600 interface. The study of interactions at the interface between Teflon AF1600 and copper deposited by different metallization techniques permitted us to elucidate some aspects related to the chemistry and structure of

  4. X-ray photoelectron spectroscopy and luminescent properties of Y2O3:Bi3+ phosphor

    NASA Astrophysics Data System (ADS)

    Jafer, R. M.; Coetsee, E.; Yousif, A.; Kroon, R. E.; Ntwaeaborwa, O. M.; Swart, H. C.

    2015-03-01

    X-ray photoelectron spectroscopy (XPS) results provided proof for the blue and green emission of Bi3+ in the Y2O3:Bi3+ phosphor. The Y2O3:Bi3+ phosphor was successfully prepared by the combustion process during the investigation of down-conversion materials for Si solar cell application. The X-ray diffraction (XRD) patterns indicated that a single-phase cubic crystal structure with the Ia3 space group was formed. X-ray photoelectron spectroscopy (XPS) showed that the Bi3+ ion replaces the Y3+ ion in two different coordination sites in the Y2O3 crystal structure. The O 1s peak shows five peaks, two which correlate with the O2- ion in Y2O3 in the two different sites, two which correlate with O2- in Bi2O3 in the two different sites and the remaining peak relates to hydroxide. The Y 3d spectrum shows two peaks for the Y3+ ion in the Y2O3 structure in two different sites and the Bi 4f spectrum shows the Bi3+ ion in the two different sites in Bi2O3. The photoluminescence (PL) results showed three broad emission bands in the blue and green regions under ultraviolet excitation, which were also present for panchromatic cathodoluminescence (CL) results. These three peaks have maxima at ∼3.4, 3.0 and 2.5 eV. The PL emission ∼3.0 eV (blue emission) showed two excitation bands centered at ∼3.7 and 3.4 eV while the PL emission at ∼2.5 eV (green emission) showed a broad excitation band from ∼4 to 3.4 eV. The panchromatic CL images were obtained for selected wavelengths at (2.99 ± 0.08) eV (for blue emission) and (2.34 ± 0.06) eV (for green emission). These luminescence results correlate with the XPS results that show that there are two different Bi3+ sites in the host lattice.

  5. Uniqueness plots: A simple graphical tool for identifying poor peak fits in X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Singh, Bhupinder; Diwan, Anubhav; Jain, Varun; Herrera-Gomez, Alberto; Terry, Jeff; Linford, Matthew R.

    2016-11-01

    Peak fitting is an essential part of X-ray photoelectron spectroscopy (XPS) narrow scan analysis, and the Literature contains both good and bad examples of peak fitting. A common cause of poor peak fitting is the inclusion of too many fit parameters, often without a sound chemical and/or physical basis for them, and/or the failure to reasonably constrain them. Under these conditions, fit parameters are often correlated, and therefore lacking in statistical meaning. Here we introduce the uniqueness plot as a simple graphical tool for identifying bad peak fits in XPS, i.e., fit parameter correlation. These plots are widely used in spectroscopic ellipsometry. We illustrate uniqueness plots with two data sets: a C 1s narrow scan from ozone-treated carbon nanotube forests and an Si 2p narrow scan from an air-oxidized silicon wafer. For each fit, we consider different numbers of parameters and constraints on them. As expected, the uniqueness plots are parabolic when fewer fit parameters and/or more constraints are applied. However, they fan out and eventually become horizontal lines as more unconstrained parameters are included in the fits. Uniqueness plots are generated by plotting the chi squared (χ2) value for a fit vs. a systematically varied value of a parameter in the fit. The Abbe criterion is also considered as a figure of merit for uniqueness plots in the Supporting Information. We recommend that uniqueness plots be used by XPS practitioners for identifying inappropriate peak fits.

  6. XPS-XRF hybrid metrology enabling FDSOI process

    NASA Astrophysics Data System (ADS)

    Hossain, Mainul; Subramanian, Ganesh; Triyoso, Dina; Wahl, Jeremy; Mcardle, Timothy; Vaid, Alok; Bello, A. F.; Lee, Wei Ti; Klare, Mark; Kwan, Michael; Pois, Heath; Wang, Ying; Larson, Tom

    2016-03-01

    Planar fully-depleted silicon-on-insulator (FDSOI) technology potentially offers comparable transistor performance as FinFETs. pFET FDOSI devices are based on a silicon germanium (cSiGe) layer on top of a buried oxide (BOX). Ndoped interfacial layer (IL), high-k (HfO2) layer and the metal gate stacks are then successively built on top of the SiGe layer. In-line metrology is critical in precisely monitoring the thickness and composition of the gate stack and associated underlying layers in order to achieve desired process control. However, any single in-line metrology technique is insufficient to obtain the thickness of IL, high-k, cSiGe layers in addition to Ge% and N-dose in one single measurement. A hybrid approach is therefore needed that combines the capabilities of more than one measurement technique to extract multiple parameters in a given film stack. This paper will discuss the approaches, challenges, and results associated with the first-in-industry implementation of XPS-XRF hybrid metrology for simultaneous detection of high-k thickness, IL thickness, N-dose, cSiGe thickness and %Ge, all in one signal measurement on a FDSOI substrate in a manufacturing fab. Strong correlation to electrical data for one or more of these measured parameters will also be presented, establishing the reliability of this technique.

  7. A photoelectron spectroscopy and thermal desorption study of CO on FeAl(110) and polycrystalline TiAl and NiAl

    NASA Astrophysics Data System (ADS)

    Gleason, N. R.; Strongin, D. R.

    1993-10-01

    Research presented in this paper investigates the electronic properties and surface reactivity of FeAl(110) and polycrystalline TiAl and NiAl toward carbon monoxide. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) have been used to characterize the electronic structure of the clean and CO-exposed surfaces. Temperature programmed desorption (TPD) shows CO desorption states below 470 K on all the aluminide surfaces. UPS shows that CO adsorption is molecular on FeAl(110) and NiAl at 130 and 200 K, respectively. The majority of CO is found to be dissociated on TiAl at 200 K. Adsorption of CO on FeAl(110) at 315 K results in both molecular and dissociated species, as determined by XPS. Heating this CO/FeAl(110) system results in further dissociation and CO desorption near 430 K. XPS data suggests that surface oxygen, resulting from CO dissociation, preferentially binds to the aluminum component.

  8. Angle resolved photoelectron spectroscopy of two-color XUV–NIR ionization with polarization control

    NASA Astrophysics Data System (ADS)

    Düsterer, S.; Hartmann, G.; Babies, F.; Beckmann, A.; Brenner, G.; Buck, J.; Costello, J.; Dammann, L.; De Fanis, A.; Geßler, P.; Glaser, L.; Ilchen, M.; Johnsson, P.; Kazansky, A. K.; Kelly, T. J.; Mazza, T.; Meyer, M.; Nosik, V. L.; Sazhina, I. P.; Scholz, F.; Seltmann, J.; Sotoudi, H.; Viefhaus, J.; Kabachnik, N. M.

    2016-08-01

    Electron emission caused by extreme ultraviolet (XUV) radiation in the presence of a strong near infrared (NIR) field leads to multiphoton interactions that depend on several parameters. Here, a comprehensive study of the influence of the angle between the polarization directions of the NIR and XUV fields on the two-color angle-resolved photoelectron spectra of He and Ne is presented. The resulting photoelectron angular distribution strongly depends on the orientation of the NIR polarization plane with respect to that of the XUV field. The prevailing influence of the intense NIR field over the angular emission characteristics for He(1s) and Ne(2p) ionization lines is shown. The underlying processes are modeled in the frame of the strong field approximation (SFA) which shows very consistent agreement with the experiment reaffirming the power of the SFA for multicolor-multiphoton ionization in this regime.

  9. Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions.

    PubMed

    Xie, Hua; Qin, Zhengbo; Wu, Xia; Tang, Zichao; Jiang, Ling

    2012-08-14

    A set of silver-doped lead Zintl anions, Ag@Pb(n)(-) (n = 5-12), have been studied using photoelectron velocity-map imaging spectroscopy and quantum chemical calculation. The structures of Ag@Pb(n)(-) (n = 7-9, 11) built upon a square pyramid base, hitherto not considered, were assigned. Overall agreement between the experimental and calculated photoelectron spectra as well as vertical detachment energies allows for structural evolution to be established. The silver atom prefers to stay outside in the n ≤ 6 clusters and intends to be encapsulated by the lead atoms in n > 6. A stable endohedral cage with bicapped square antiprism structure is formed at n = 10, the endohedral structure of which persists for the larger clusters. Especially, these Ag@Pb(n)(-) anions have been found to undergo a transition between square pyramid and pentagonal pyramid molecular structures at n = 11. PMID:22897284

  10. Feasibility tests of transmission x-ray photoelectron emission microscopy of wet samples

    NASA Astrophysics Data System (ADS)

    De Stasio, Gelsomina; Gilbert, B.; Nelson, T.; Hansen, R.; Wallace, J.; Mercanti, D.; Capozi, M.; Baudat, P. A.; Perfetti, P.; Margaritondo, G.; Tonner, B. P.

    2000-01-01

    We performed feasibility tests of photoelectron emission spectromicroscopy of wet samples in the water window (285-532 eV) soft x-ray spectral region. Water was successfully confined in an ultrahigh vacuum compatible compartment with x-ray transparent sides. This water cell was placed in the MEPHISTO spectromicroscope in a transmission geometry, and complete x-ray absorption spectra of the water window region were acquired. We also show micrographs of test samples, mounted outside of the compartment, and imaged through the water. This technique can be used to study liquid chemistry and, at least to the micron level, the microstructure of wet samples. Possibilities include cells in water or buffer, proteins in solution, oils of tribological interest, liquid crystals, and other samples not presently accessible to the powerful x-ray photoelectron emission spectromicroscopy technique.

  11. Angle resolved photoelectron spectroscopy of two-color XUV-NIR ionization with polarization control

    NASA Astrophysics Data System (ADS)

    Düsterer, S.; Hartmann, G.; Babies, F.; Beckmann, A.; Brenner, G.; Buck, J.; Costello, J.; Dammann, L.; De Fanis, A.; Geßler, P.; Glaser, L.; Ilchen, M.; Johnsson, P.; Kazansky, A. K.; Kelly, T. J.; Mazza, T.; Meyer, M.; Nosik, V. L.; Sazhina, I. P.; Scholz, F.; Seltmann, J.; Sotoudi, H.; Viefhaus, J.; Kabachnik, N. M.

    2016-08-01

    Electron emission caused by extreme ultraviolet (XUV) radiation in the presence of a strong near infrared (NIR) field leads to multiphoton interactions that depend on several parameters. Here, a comprehensive study of the influence of the angle between the polarization directions of the NIR and XUV fields on the two-color angle-resolved photoelectron spectra of He and Ne is presented. The resulting photoelectron angular distribution strongly depends on the orientation of the NIR polarization plane with respect to that of the XUV field. The prevailing influence of the intense NIR field over the angular emission characteristics for He(1s) and Ne(2p) ionization lines is shown. The underlying processes are modeled in the frame of the strong field approximation (SFA) which shows very consistent agreement with the experiment reaffirming the power of the SFA for multicolor-multiphoton ionization in this regime.

  12. Time-dependent photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    Wang, Xiangyang

    1999-09-01

    I show that the angular distribution of electrons photoionized from gas phase targets by short light pulses is time-dependent, when the orbital momentum composition of the photocurrent changes with excitation energy so evolves with the time of detection. A theory of time- dependent photoionization is outlined and general formulas of time-dependent photoelectron flux and angular distribution are given. Two general propagator methods suitable to describe the time-dependent photoionization and scattering processes are developed. The photoionization process is viewed as a local excitation followed by a half scattering. The local excitation process is solved theoretically in a small region around the target core. This approach has been generalized to describe the evolution of a wavepacket in an unbound system. An asymptotic propagator theorem is discovered and used to derive analytic expressions for asymptotic propagators. The origin of the time dependence is explored by parameterizing the time delay and orbital momentum coupling in a two channel model. K-shell photoionization of N2 and CO are calculated with this time- dependent photoionization theory, implemented using a multiple scattering model. Numerical results demonstrate that the time dependence of photoelectron angular distributions is a realistic effect.

  13. Photoelectron Spectroscopy of Multiply Charged Anions

    SciTech Connect

    Wang, Xue B.; Wang, Lai S.

    2009-07-01

    Multiply charged anions (MCA’s) are common in the condensed phases, but are challenging to study in the gas phase. An experimental technique coupling photoelectron spectroscopy (PES) with electrospray ionization (ESI) has been developed to investigate properties of free MCA’s in the gas phase. In this article, the principles of this technique, and some initial findings about the intrinsic properties of MCA’s are reviewed. Examples chosen include the observation of the repulsive Coulomb barrier that exists universally in MCA’s and its effects on the dynamic stability and photoelectron spectroscopy of MCA’s. Solvation and solvent stabilization of MCA’s has been studied in the gas phase and will also be discussed. A second generation low-temperature ESI-PES apparatus has been developed, which allows ion temperatures to be controlled between 10 to 350 K. New results from the low-temperature ESI-PES instrument will also be reviewed, including doubly charged fullerene anions, inorganic metal complexes, and temperature-induced conformation changes of complex anions.

  14. Vibrational Cooling in A Cold Ion Trap: Vibrationally Resolved Photoelectron Spectroscopy of Cold C60- Anions

    SciTech Connect

    Wang, Xue B.; Woo, Hin-koon; Wang, Lai S.

    2005-08-01

    We demonstrate vibrational cooling of anions via collisions with a background gas in an ion trap attached to a cryogenically controlled cold head (10 ? 400 K). Photoelectron spectra of vibrationally cold C60- anions, produced by electrospray ionization and cooled in the cold ion trap, have been obtained. Relative to spectra taken at room temperature, vibrational hot bands are completely eliminated, yielding well resolved vibrational structures and a more accurate electron affinity for neutral C60. The electron affinity of C60 is measured to be 2.683 ? 0.008 eV. The cold spectra reveal complicated vibrational structures for the transition to the C60 ground state due to the Jahn-Teller effect in the ground state of C60-. Vibrational excitations in the two Ag modes and eight Hg modes are observed, providing ideal data to assess the vibronic couplings in C60-.

  15. A chemical, morphological, and electrochemical (XPS, SEM/EDX, CV, and EIS) analysis of electrochemically modified electrode surfaces of natural chalcopyrite (CuFeS2) and pyrite (FeS2) in alkaline solutions.

    PubMed

    Velásquez, Pablo; Leinen, Dietmar; Pascual, José; Ramos-Barrado, José Ramón; Grez, Paula; Gómez, Humberto; Schrebler, Ricardo; Del Río, Rodrigo; Córdova, Ricardo

    2005-03-24

    Electrodic surfaces of natural chalcopyrite and natural pyrite minerals (El Teniente mine, Chile) have been studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy including microanalysis (SEM/EDX). For comparison, fractured and polished mineral surfaces were also studied by XPS. In both electrodes, the formation of Fe(III) species containing oxygen were detected and Cu(II) species containing oxygen were additionally detected for chalcopyrite at advanced oxidation states. The presence of Cu(II) species containing oxygen was not detected by XPS for the initial oxidation states of the chalcopyrite. For pyrite, the present results do not allow confirmation of the presence of polysulfurs such as have been previously proposed. In both minerals, the measurements of SEM and EDX show relevant alterations in the respective surfaces when different potential values were applied. The chalcopyrite surface shows the formation of protrusions with a high concentration of oxygen. The pyrite surface shows a layer of modified material with high oxygen content. The modifications detected by XPS, SEM, and EDX allowed the explanation of the complexity of the equivalent circuit used to simulate the experimental EIS data. At high oxidation states, both minerals showed a pseudoinductive loop in the equivalent circuit, which was due to the active electrodissolution of the minerals which takes place through a surface film previously formed. PMID:16863157

  16. A chemical, morphological, and electrochemical (XPS, SEM/EDX, CV, and EIS) analysis of electrochemically modified electrode surfaces of natural chalcopyrite (CuFeS2) and pyrite (FeS2) in alkaline solutions.

    PubMed

    Velásquez, Pablo; Leinen, Dietmar; Pascual, José; Ramos-Barrado, José Ramón; Grez, Paula; Gómez, Humberto; Schrebler, Ricardo; Del Río, Rodrigo; Córdova, Ricardo

    2005-03-24

    Electrodic surfaces of natural chalcopyrite and natural pyrite minerals (El Teniente mine, Chile) have been studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy including microanalysis (SEM/EDX). For comparison, fractured and polished mineral surfaces were also studied by XPS. In both electrodes, the formation of Fe(III) species containing oxygen were detected and Cu(II) species containing oxygen were additionally detected for chalcopyrite at advanced oxidation states. The presence of Cu(II) species containing oxygen was not detected by XPS for the initial oxidation states of the chalcopyrite. For pyrite, the present results do not allow confirmation of the presence of polysulfurs such as have been previously proposed. In both minerals, the measurements of SEM and EDX show relevant alterations in the respective surfaces when different potential values were applied. The chalcopyrite surface shows the formation of protrusions with a high concentration of oxygen. The pyrite surface shows a layer of modified material with high oxygen content. The modifications detected by XPS, SEM, and EDX allowed the explanation of the complexity of the equivalent circuit used to simulate the experimental EIS data. At high oxidation states, both minerals showed a pseudoinductive loop in the equivalent circuit, which was due to the active electrodissolution of the minerals which takes place through a surface film previously formed.

  17. X-ray photoelectron spectroscopy of copper(II), copper(I), and mixed valence systems.

    PubMed

    Rupp, H; Weser, U

    1976-01-01

    X-ray photoelectron spectroscopy using copper(II), copper(I) and the mixed valence Cu(II)/Cu(I) compounds was employed as a means of studying electron transfer reactions in copper proteins. The X-ray photoelectron spectra of copper(II) compounds display characteristic satellites of both variable size and resolution. Some of these satellites could be assigned to specific ligand interactions. Unlike electron paramagnetic resonance spectroscopy, the X-ray photoelectron spectroscopic measurements of copper(I) compounds allowed the unequivocal assignment of this oxidation state. No satellites at all could be detected in the Cu(I) spectra. Furthermore, established mixed valence Cu(II)/Cu(I) complexes including Cu2SO3-CuSO3-2H2O and Cu4Cl5 (ethylenediamine)2 proved essentially a mixture of distinct portions of Cu(I) and Cu(II). This indicates that both oxidation states of copper survive in such complexes. In contrast, all Cu X-ray photoelectron signals of the more tentatively described mixed valence complexes Na2Cu3S3 and the mineral covellite, CuI4CuII2(S2)2S2, could be attributed exclusively to Cu(I). In view of the known binding of copper with sulfur in many copper proteins, it was of utmost importance to study the copper-sulfur interactions. We have demonstrated the absence of Cu(II) in CuS. This indicates strong metal-induced polarization of sulfur resulting in electron transfer to copper to yield Cu(I). PMID:953045

  18. Oxidation of α-brass: A photoelectron spectroscopy study

    NASA Astrophysics Data System (ADS)

    Wiame, Frédéric; Jasnot, François-Régis; Światowska, Jolanta; Seyeux, Antoine; Bertran, François; Le Fèvre, Patrick; Taleb-Ibrahimi, Amina; Maurice, Vincent; Marcus, Philippe

    2015-11-01

    The oxidation of Cu0.7Zn0.3(111) exposed to O2 at low pressure (7.0 × 10- 7 mbar) and higher pressure (1 mbar) both at 400 K has been investigated by photoelectron spectroscopy. The results evidenced a preferential oxidation of Zn at the surface in agreement with the literature and Zn segregation to the surface. Moreover, a systematic fitting procedure of high-resolution spectra enabled us to decompose the Zn 2p core-level peak into metallic and oxide components in order to follow the growth of the oxide. By combining these results with careful analysis of the Zn L3M45M45 Auger transition, we evidenced the formation of a discontinuous ZnO layer (3D ZnO islands) in both pressure conditions. Measurements of the O 1s peak for two photon energies using synchrotron radiation allowed us to identify interface and bulk components. Changes in the Zn 3d level and valence band during the initial steps of oxidation were also followed. We show that not only thermodynamics but also kinetic effects have to be considered to describe this complex oxidation process. The importance of the role played by the structural quality of the sample on the composition, growth kinetic and structure of the surface oxide layer is evidenced.

  19. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission.

    PubMed

    Sen, Ananya; Matthews, Edward M; Hou, Gao-Lei; Wang, Xue-Bin; Dessent, Caroline E H

    2015-11-14

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 (2-) dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 (2-) ⋅ thymine and PtCl6 (2-) ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 (2-) ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl6 (2-) ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 (2-) ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a "dynamic tag" which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to allow autodetachment.

  20. Photoelectron Spectroscopy of Hexachloroplatinate-Nucleobase Complexes: Nucleobase Excited State Decay Observed via Delayed Electron Emission

    SciTech Connect

    Sen, Ananya; Matthews, Edward M.; Hou, Gao-Lei; Wang, Xue B.; Dessent, Caroline

    2015-11-14

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ~1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 2- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 2-∙thymine and PtCl6 2-∙adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 2-∙nucleobase complexes [Sen et al, J. Phys. Chem. B, 119, 11626, 2015]. The observation of delayed electron emission bands in the PtCl6 2-∙nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 2-∙nucleobase complexes, is attributed to onephoton excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a timescale long enough to allow autodetachment.

  1. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission.

    PubMed

    Sen, Ananya; Matthews, Edward M; Hou, Gao-Lei; Wang, Xue-Bin; Dessent, Caroline E H

    2015-11-14

    We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 (2-) dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 (2-) ⋅ thymine and PtCl6 (2-) ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 (2-) ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl6 (2-) ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 (2-) ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a "dynamic tag" which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to allow autodetachment. PMID:26567662

  2. Photoelectron spectroscopy of GaX2-, Ga2X-, Ga2X2-, and Ga2X3-(X=P,As)

    NASA Astrophysics Data System (ADS)

    Taylor, Travis R.; Gómez, Harry; Asmis, Knut R.; Neumark, Daniel M.

    2001-09-01

    Anion photoelectron spectra taken at various photodetachment wavelengths have been obtained for GaX2-, Ga2X-, Ga2X2-, and Ga2X3- (X=P,As). The incorporation of a liquid nitrogen cooled channel in the ion source resulted in substantial vibrational cooling of the cluster anions, resulting in resolved vibrational progressions in the photoelectron spectra of all species except Ga2X2-. Electron affinities, electronic term values, and vibrational frequencies are reported and compared to electronic structure calculations. In addition, similarities and differences between the phosphorus and arsenic-containing isovalent species are discussed.

  3. Thermally Evaporated Iron (Oxide) on an Alumina Barrier Layer, by XPS

    SciTech Connect

    Madaan, Nitesh; Kanyal, Supriya S.; Jensen, David S.; Vail, Michael A.; Dadson, Andrew; Engelhard, Mark H.; Linford, Matthew R.

    2013-09-06

    We report the XPS characterization of a thermally evaporated iron thin film (6 nm) deposited on an Si/SiO_2/Al_2O_3 substrate using Al Ka X-rays. An XPS survey spectrum, narrow Fe 2p scan, narrow O 1s, and valence band scan are shown.

  4. [XPS analysis of tea plant leaf and root surface].

    PubMed

    Fang, Jiang-yu; Wan, Xiao-chun

    2008-09-01

    XPS was applied to analyze the surface chemical composition and structure of the tea plant leaf and root. It was detected that the surface is made up of mainly 4 elements: C, O, N and Al, with little P and F in abaxial leaf. Based on the botanic epidermis structure and the chemical composition, with the help of the standard spectrum data bank on line and the wood XPS study results, and through line Gaussian and Lorentizian the mixed, the binding energy of C(1s) of the leaf surface was classified as 3 types: the first was C1, with the electron binding energy of 285 eV, from C-C or C-H group, representing lipid compound like cutin and wax. C2 with the binding energy of 286.35 eV in the adaxial and 286.61 eV in the abaxial, came from the single bond of carbon and oxygen C-O, mainly standing for cellulose. C3 with the binding energy of approximately 288 eV (288.04 eV in adaxial and 288.09 eV in abaxial) was the sign of C=O group, which is acyl in protein with the confirmation of N(1s) (399-401 eV)and O(1s) analyses. In the root surface, besides the same compounds of cutin and wax (C1, binding energy 285 eV), cellulose (C2, binding energy 286.49 eV) and protein (C3, binding energy 288.78 eV)as in the leaf, there appeared C5 type with the binding energy of 283.32 eV. Because it was lower than C1, it was estimated as carbon linking to metal. Both the leaf and the root surfaces didn't have C4, a type of O-C=O, which is common in wood surface with the highest oxidated carbon of 289-289.5 eV binding energy, indicating that organic acid secreted by the root existed freely on the root surface, without any chemical association with the surface compounds. The results of the separated spectrum of O(1s) supported the above C(1s) results. By the ratio of each type of C, there were more oxygen groups in the abaxial than in the adaxial, implicating more active chemical properties on the abaxial. Compared with the leaf, cutin and wax was little in the root and oxygen groups were many

  5. Ellipsometry and XPS comparative studies of thermal and plasma enhanced atomic layer deposited Al2O3-films

    PubMed Central

    Haeberle, Jörg; Gargouri, Hassan; Naumann, Franziska; Gruska, Bernd; Arens, Michael; Tallarida, Massimo; Schmeißer, Dieter

    2013-01-01

    Summary We report on results on the preparation of thin (<100 nm) aluminum oxide (Al2O3) films on silicon substrates using thermal atomic layer deposition (T-ALD) and plasma enhanced atomic layer deposition (PE-ALD) in the SENTECH SI ALD LL system. The T-ALD Al2O3 layers were deposited at 200 °C, for the PE-ALD films we varied the substrate temperature range between room temperature (rt) and 200 °C. We show data from spectroscopic ellipsometry (thickness, refractive index, growth rate) over 4” wafers and correlate them to X-ray photoelectron spectroscopy (XPS) results. The 200 °C T-ALD and PE-ALD processes yield films with similar refractive indices and with oxygen to aluminum elemental ratios very close to the stoichiometric value of 1.5. However, in both also fragments of the precursor are integrated into the film. The PE-ALD films show an increased growth rate and lower carbon contaminations. Reducing the deposition temperature down to rt leads to a higher content of carbon and CH-species. We also find a decrease of the refractive index and of the oxygen to aluminum elemental ratio as well as an increase of the growth rate whereas the homogeneity of the film growth is not influenced significantly. Initial state energy shifts in all PE-ALD samples are observed which we attribute to a net negative charge within the films. PMID:24367741

  6. Adsorption of sodium dodecyl sulfate and sodium dodecyl phosphate on aluminum, studied by QCM-D, XPS, and AAS.

    PubMed

    Karlsson, Philip M; Palmqvist, Anders E C; Holmberg, Krister

    2008-12-01

    The adsorption of two anionic surfactants, sodium dodecyl sulfate (SDS) and sodium dodecyl phosphate (SDP), at surfaces of aluminum and aluminum oxide has been studied by means of atomic absorption spectrometry (AAS), X-ray photoelectron spectroscopy (XPS), and quartz crystal microbalance with dissipation monitoring (QCM-D). It was shown that more SDP than SDS binds to the surface and that SDP prevents dissolution of aluminum in water whereas SDS does not. This was not obvious, since the adsorption isotherms of the two surfactants to aluminum pigment powder are quite similar, as shown in an earlier work. The decreased aluminum dissolution with SDP compared to SDS was explained by the formation of a more compact protective layer with less permeability on the aluminum surface with SDP than with SDS. This is explained by differences in complexing ability between the surfactants and the aluminum pigment surface. While SDP is expected to form an inner-sphere complex with aluminum, leading to a lower accessibility of aluminum sites to water, SDS is likely to form a weaker outer-sphere complex.

  7. Assessment of novel chemical strategies for covalent attachment of adhesive peptides to rough titanium surfaces: XPS analysis and biological evaluation.

    PubMed

    Dettin, Monica; Herath, Thushari; Gambaretto, Roberta; Iucci, Giovanna; Battocchio, Chiara; Bagno, Andrea; Ghezzo, Francesca; Di Bello, Carlo; Polzonetti, Giovanni; Di Silvio, Lucy

    2009-11-01

    Bioactive molecules have been proposed to promote beneficial interactions at bone-implant interfaces for enhancing integration. The main objective of this study was to develop novel methods to functionalize oxidized titanium surfaces by the covalent immobilization of bioactive peptides, through selective reaction involving single functional groups. In the first protocol, an aminoalkylsilane was covalently linked to the Ti oxide layer, followed by covalent binding of glutaric anhydride to the free NH(2) groups. The carboxylic group of glutaric anhydride was used to condense the free N-terminal group of the side-chain protected peptide sequence. Finally, the surface was treated with trifluoroacetic acid to deprotect side-chain groups. In the second protocol, the peptide was directly anchored to the Ti oxide surface via UV activation of an arylazide peptide analogue. X-ray photoelectron spectroscopy analyses confirmed that modifications induced onto surface composition were in agreement with the reactions performed. The peptide density of each biomimetic surface was determined on the basis of radiolabeling and XPS derived reaction yields. The in vitro cellular response of the biomimetic surfaces was evaluated using a primary human osteoblast cell model. Cell adhesion, proliferation, differentiation, and mineralization were examined at initial-, short-, and long-time periods. In was shown that the biomimetic surface obtained through photoprobe-marked analogue that combines an easily-performed modification provides a favorable surface for an enhanced cellular response.

  8. AFM, ellipsometry, XPS and TEM on ultra-thin oxide/polymer nanocomposite layers in organic thin film transistors.

    PubMed

    Fian, A; Haase, A; Stadlober, B; Jakopic, G; Matsko, N B; Grogger, W; Leising, G

    2008-03-01

    Here we report on the fabrication and characterization of ultra-thin nanocomposite layers used as gate dielectric in low-voltage and high-performance flexible organic thin film transistors (oTFTs). Reactive sputtered zirconia layers were deposited with low thermal exposure of the substrate and the resulting porous oxide films with high leakage currents were spin-coated with an additional layer of poly-alpha-methylstyrene (P alphaMS). After this treatment a strong improvement of the oTFT performance could be observed; leakage currents could be eliminated almost completely. In ellipsometric studies a higher refractive index of the ZrO(2)/P alphaMS layers compared to the "as sputtered" zirconia films could be detected without a significant enhancement of the film thickness. Atomic force microscopy (AFM) measurements of the surface topography clearly showed a surface smoothing after the P alphaMS coating. Further studies with X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) also indicated that the polymer definitely did not form an extra layer. The polymer chains rather (self-)assemble in the nano-scaled interspaces of the porous oxide film giving an oxide-polymer "nanocomposite" with a high oxide filling grade resulting in high dielectric constants larger than 15. The dielectric strength of more than 1 MV cm(-1) is in good accordance with the polymer-filled interspaces. PMID:17952415

  9. Evaluation Metrics for the Paragon XP/S-15

    NASA Technical Reports Server (NTRS)

    Traversat, Bernard; McNab, David; Nitzberg, Bill; Fineberg, Sam; Blaylock, Bruce T. (Technical Monitor)

    1993-01-01

    On February 17th 1993, the Numerical Aerodynamic Simulation (NAS) facility located at the NASA Ames Research Center installed a 224 node Intel Paragon XP/S-15 system. After its installation, the Paragon was found to be in a very immature state and was unable to support a NAS users' workload, composed of a wide range of development and production activities. As a first step towards addressing this problem, we implemented a set of metrics to objectively monitor the system as operating system and hardware upgrades were installed. The metrics were designed to measure four aspects of the system that we consider essential to support our workload: availability, utilization, functionality, and performance. This report presents the metrics collected from February 1993 to August 1993. Since its installation, the Paragon availability has improved from a low of 15% uptime to a high of 80%, while its utilization has remained low. Functionality and performance have improved from merely running one of the NAS Parallel Benchmarks to running all of them faster (between 1 and 2 times) than on the iPSC/860. In spite of the progress accomplished, fundamental limitations of the Paragon operating system are restricting the Paragon from supporting the NAS workload. The maximum operating system message passing (NORMA IPC) bandwidth was measured at 11 Mbytes/s, well below the peak hardware bandwidth (175 Mbytes/s), limiting overall virtual memory and Unix services (i.e. Disk and HiPPI I/O) performance. The high NX application message passing latency (184 microns), three times than on the iPSC/860, was found to significantly degrade performance of applications relying on small message sizes. The amount of memory available for an application was found to be approximately 10 Mbytes per node, indicating that the OS is taking more space than anticipated (6 Mbytes per node).

  10. XPS chemical analysis of tholins: the oxygen contamination

    NASA Astrophysics Data System (ADS)

    Carrasco, N.; Jomard, F.; Vigneron, J.; Cernogora, G.

    2013-12-01

    In Titan's atmosphere, solid organic aerosols are initiated in the upper atmosphere by the photo-dissociation and photo-ionization of N2 and CH4. In order to simulate this complex chemistry several experimental setups have been built, among them plasma experiments. The aerosol analogues produced in such plasma discharges contain oxygen, as a few percents of the elemental composition, despite the absence of oxygen source in the reactive medium [1]. The present study aims at studying the origin of such systematic oxygen incorporation in tholins. A low pressure (0.9mbar) RF CCP discharge is used described in [2]. Gas mixtures of N2 and CH4 (from 1 to 10% of CH4) are injected continuously. The plasma discharge leads to the production of analogues of Titan's atmospheric aerosols: both as grains in the volume [1] and as thin films on the surface of the reactor [3]. SiO2 substrates of 1cm diameter and 1mm thickness are placed on the grounded electrode of the discharge. Organic films are deposited during 2 hours in order to have films thickness less than 1μm. After the two hours, samples are recovered at ambient air for ex-situ analysis. Two complementary analyses are performed to analyse the thin film chemical composition: XPS and SIMS, in order to probe both the surface and depth profile. References [1] Sciamma-O'brien E., Carrasco N., Szopa C., Buch A., Cernogora G. Icarus 209, 2 (2010) 704-714 [2] Alcouffe G., Cavarroc M., Cernogora G., Ouni F., Jolly A., Boufendi L., Szopa C. Plasma Sources Science and Technology 19, 1 (2010) 015008 (11pp) [3] Mahjoub A., Carrasco N., Dahoo P.-R., Gautier T., Szopa C., Cernogora G. Icarus 221, 2 (2012) 670-677.

  11. Isomer-selected photoelectron spectroscopy of isolated DNA oligonucleotides: phosphate and nucleobase deprotonation at high negative charge states.

    PubMed

    Vonderach, Matthias; Ehrler, Oli T; Matheis, Katerina; Weis, Patrick; Kappes, Manfred M

    2012-05-01

    Fractionation according to ion mobility and mass-to-charge ratio has been used to select individual isomers of deprotonated DNA oligonucleotide multianions for subsequent isomer-resolved photoelectron spectroscopy (PES) in the gas phase. Isomer-resolved PE spectra have been recorded for tetranucleotides, pentanucleotides, and hexanucleotides. These were studied primarily in their highest accessible negative charge states (3-, 4-, and 5-, respectively), as provided by electrospraying from room temperature solutions. In particular, the PE spectra obtained for pentanucleotide tetraanions show evidence for two coexisting classes of gas-phase isomeric structures. We suggest that these two classes comprise: (i) species with excess electrons localized exclusively at deprotonated phosphate backbone sites and (ii) species with at least one deprotonated base (in addition to several deprotonated phosphates). By permuting the sequence of bases in various [A(5-x)T(x)](4-) and [GT(4)](4-) pentanucleotides, we have established that the second type of isomer is most likely to occur if the deprotonated base is located at the first or last position in the sequence. We have used a combination of molecular mechanics and semiempirical calculations together with a simple electrostatic model to explore the photodetachment mechanism underlying our photoelectron spectra. Comparison of predicted to measured photoelectron spectra suggests that a significant fraction of the detected electrons originates from the DNA bases (both deprotonated and neutral).

  12. Isomer-selected photoelectron spectroscopy of isolated DNA oligonucleotides: phosphate and nucleobase deprotonation at high negative charge states.

    PubMed

    Vonderach, Matthias; Ehrler, Oli T; Matheis, Katerina; Weis, Patrick; Kappes, Manfred M

    2012-05-01

    Fractionation according to ion mobility and mass-to-charge ratio has been used to select individual isomers of deprotonated DNA oligonucleotide multianions for subsequent isomer-resolved photoelectron spectroscopy (PES) in the gas phase. Isomer-resolved PE spectra have been recorded for tetranucleotides, pentanucleotides, and hexanucleotides. These were studied primarily in their highest accessible negative charge states (3-, 4-, and 5-, respectively), as provided by electrospraying from room temperature solutions. In particular, the PE spectra obtained for pentanucleotide tetraanions show evidence for two coexisting classes of gas-phase isomeric structures. We suggest that these two classes comprise: (i) species with excess electrons localized exclusively at deprotonated phosphate backbone sites and (ii) species with at least one deprotonated base (in addition to several deprotonated phosphates). By permuting the sequence of bases in various [A(5-x)T(x)](4-) and [GT(4)](4-) pentanucleotides, we have established that the second type of isomer is most likely to occur if the deprotonated base is located at the first or last position in the sequence. We have used a combination of molecular mechanics and semiempirical calculations together with a simple electrostatic model to explore the photodetachment mechanism underlying our photoelectron spectra. Comparison of predicted to measured photoelectron spectra suggests that a significant fraction of the detected electrons originates from the DNA bases (both deprotonated and neutral). PMID:22524691

  13. An XPS study of passive films on stainless steels and a high-grade Ni-base alloy in seawater environments

    SciTech Connect

    Hodgkiess, T.; Neville, A.

    1999-11-01

    In the present study an assessment has been made of the air-formed passive film and the passive film existing after a short exposure to a synthetic seawater environment on austenitic (UNS S31603), superaustenitic (UNS S31254 and UNS S32654) and superduplex (UNS S32760) stainless steels and a Ni-based alloy (UNS N06625) using X-Ray Photoelectron Spectroscopy (XPS). Assessment of their corrosion behavior has been made through use of electrochemical accelerated tests supported by post-test microscopy. The passive film on the Ni-base (low Fe) UNS N06625 alloy is remarkably similar to those formed on the high Cr and Mo stainless steels. It has been demonstrated that the Fe/Cr ratio in the passive film is dependent on alloy composition and on the conditions to which the material has been exposed and a general correlation between passive film constitution and corrosion resistance is evident.

  14. Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

    PubMed Central

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-01-01

    In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

  15. Surface chemistry of SnO2 nanowires on Ag-catalyst-covered Si substrate studied using XPS and TDS methods

    PubMed Central

    2014-01-01

    In this paper we investigate the surface chemistry, including surface contaminations, of SnO2 nanowires deposited on Ag-covered Si substrate by vapor phase deposition (VPD), thanks to x-ray photoelectron spectroscopy (XPS) in combination with thermal desorption spectroscopy (TDS). Air-exposed SnO2 nanowires are slightly non-stoichiometric, and a huge amount of C contaminations is observed at their surface. After the thermal physical desorption (TPD) process, SnO2 nanowires become almost stoichiometric without any surface C contaminations. This is probably related to the fact that C contaminations, as well as residual gases from air, are weakly bounded to the crystalline SnO2 nanowires and can be easily removed from their surface. The obtained results gave us insight on the interpretation of the aging effect of SnO2 nanowires that is of great importance for their potential application in the development of novel chemical nanosensor devices. PMID:24461127

  16. The relationship between the surface composition and electrical properties of corrosion films formed on carbon steel in alkaline sour medium: an XPS and EIS study.

    PubMed

    Galicia, Policarpo; Batina, Nikola; González, Ignacio

    2006-07-27

    This work studies the evolution of 1018 carbon steel surfaces during 3-15 day immersion in alkaline sour medium 0.1 M (NH4)2S and 10 ppm CN(-) as (NaCN). During this period of time, surfaces were jointly characterized by electrochemical techniques in situ (electrochemical impedance spectroscopy, EIS) and spectroscopic techniques ex situ (X-ray photoelectron spectroscopy, XPS). The results obtained by these techniques allowed for a description of electrical and chemical properties of the films of corrosion products formed at the 1018 steel surface. There is an interconversion cycle of chemical species that form films of corrosion products whose conversion reactions favor two different types of diffusions inside the films: a chemical diffusion of iron cations and a typical diffusion of atomic hydrogen. These phenomena jointly control the passivity of the interface attacked by the corrosive medium.

  17. XPS-nanocharacterization of organic layers electrochemically grafted on the surface of SnO2 thin films to produce a new hybrid material coating

    NASA Astrophysics Data System (ADS)

    Drevet, R.; Dragoé, D.; Barthés-Labrousse, M. G.; Chaussé, A.; Andrieux, M.

    2016-10-01

    This work presents the synthesis and the characterization of hybrid material thin films obtained by the combination of two processes. The electrochemical grafting of organic layers made of carboxyphenyl moieties is carried out from the reduction of a diazonium salt on tin dioxide (SnO2) thin films previously deposited on Si substrates by metal organic chemical vapor deposition (MOCVD). Since the MOCVD experimental parameters impact the crystal growth of the SnO2 layer (i.e. its morphology and its texturation), various electrochemical grafting models can occur, producing different hybrid materials. In order to evidence the efficiency of the electrochemical grafting of the carboxyphenyl moieties, X-ray Photoelectron Spectroscopy (XPS) is used to characterize the first nanometers in depth of the synthesized hybrid material layer. Then three electrochemical grafting models are proposed.

  18. Enhancing electrochemical water-splitting kinetics by polarization-driven formation of near-surface iron(0): an in situ XPS study on perovskite-type electrodes.

    PubMed

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-02-23

    In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6 Sr0.4 FeO3-δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe(0) on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity.

  19. Time-dependent investigation of sub-monolayers of Ni on Pd using Positron-annihilation induced Auger Electron Spectroscopy and XPS

    NASA Astrophysics Data System (ADS)

    Zimnik, Samantha; Piochacz, Christian; Vohburger, Sebastian; Hugenschmidt, Christoph

    2016-01-01

    The surface of a polycrystalline Pd-substrate covered with (sub-) monolayers of Ni was investigated with Positron-annihilation induced Auger Electron Spectroscopy (PAES). Comparative studies using conventional AES induced by electrons and X-rays showed the outstanding surface sensitivity of PAES. Time-dependent PAES was performed on a 0.5 ML Ni cover layer on Pd and compared with conventional X-ray induced Photoelectron Spectroscopy (XPS) in order to observe changes in the elemental composition of the surface. The PAES results appear to show a migration of Ni atoms into the Pd substrate, whereas the Ni signal shows a decrease of 12% within 13 h with respect to the initial value.

  20. Relationships Between Complex Core Level Spectra and Materials Properties

    SciTech Connect

    Nelin, Constance J.; Bagus, Paul S.; Ilton, Eugene S.; Chambers, Scott A.; Kuhlenbeck, Helmut; Freund, Hans-Joachim

    2010-12-01

    The XPS of many oxides are quite complex and there may be several peaks of significant intensity for each subshell. These peaks arise from many-electron effects, which normally are treated with configuration interaction (CI) wavefunctions where static correlation effects are taken into account. It is common to use semiempirical methods to determine the matrix elements of the CI Hamiltonian and there are few rigorous CI calculations where parameters are not adjusted to fit experiment. In contrast, we present, in the present work, theoretical XPS spectra obtained with rigorous CI wavefunctions for CeO2 where the XPS are especially complex; several different core levels are studied. This study uses an embedded CeO8 cluster model to represent bulk CeO2 and the relativistic CI wavefunctions are determined using four-component spinors from Dirac-Fock calculations. In particular, we examine the importance of interatomic many-body effects where there is a transfer of electrons from occupied oxygen 2p orbitals into empty cation orbitals as it is common to ascribe the complex XPS to this effect. We also contrast the importance of many-body charge-transfer effects for the isoelectronic cations of Ce4+ and La3+. The long-range goal of this work is to relate the XPS features to the nature of the chemical bonding in CeO2 and we describe our progress toward this goal.

  1. Probing the electronic and vibrational structure of Au{sub 2}Al{sub 2}{sup −} and Au{sub 2}Al{sub 2} using photoelectron spectroscopy and high resolution photoelectron imaging

    SciTech Connect

    Lopez, Gary V.; Czekner, Joseph; Jian, Tian; Li, Wei-Li; Yang, Zheng; Wang, Lai-Sheng

    2014-12-14

    The electronic and vibrational structures of Au{sub 2}Al{sub 2}{sup −} and Au{sub 2}Al{sub 2} have been investigated using photoelectron spectroscopy (PES), high-resolution photoelectron imaging, and theoretical calculations. Photoelectron spectra taken at high photon energies with a magnetic-bottle apparatus reveal numerous detachment transitions and a large energy gap for the neutral Au{sub 2}Al{sub 2}. Vibrationally resolved PE spectra are obtained using high-resolution photoelectron imaging for the ground state detachment transition of Au{sub 2}Al{sub 2}{sup −} at various photon energies (670.55−843.03 nm). An accurate electron affinity of 1.4438(8) eV is obtained for the Au{sub 2}Al{sub 2} neutral cluster, as well as two vibrational frequencies at 57 ± 8 and 305 ± 13 cm{sup −1}. Hot bands transitions yield two vibrational frequencies for Au{sub 2}Al{sub 2}{sup −} at 57 ± 10 and 144 ± 12 cm{sup −1}. The obtained vibrational and electronic structure information is compared with density functional calculations, unequivocally confirming that both Au{sub 2}Al{sub 2}{sup −} and Au{sub 2}Al{sub 2} possess C{sub 2v} tetrahedral structures.

  2. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    SciTech Connect

    Bradforth, S.E.

    1992-11-01

    The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus

  3. An (e,2e) Measurement of the Xe Photoelectron β Parameter

    NASA Astrophysics Data System (ADS)

    Childers, J. G.; Martin, N. L. S.; Thompson, D. B.

    2000-06-01

    We have carried out (e,2e) experiments on Xe in the autoionizing region between the ^2P_3/2 and ^2P_1/2 ionic limits. (e,2e) spectra were taken at 150 eV incident electron energy and 0^circ scattering angle corresponding to a momentum transfer of 0.14 au. The spectral range covered the (^2P_1/2)nd,ms (n>=6,m>=8) autoionizing resonances which have ejected electron energies between 0 and 1.3 eV. The (e,2e) spectrometer has two ejected electron detectors configured to allow the simultaneous collection of (e,2e) ejected-electron spectra 180^circ apart. The summation of these spectra eliminates the non-dipole effects due to dipole-monopole and dipole-quadrupole interference, leaving a spectrum that mimics a pure dipole photoelectron experiment. Two separate (e,2e) experiments, at ejected electron directions 60^circ (the minimum possible) and 90^circ away from the momentum transfer axis, enable the determination of the Xe β parameter. Our results are in quite good agreement with the true photoelectron experiments.(J.Z. Wu, S.B. Whitfield, C.D. Caldwell, M.O. Krause, P. van der Meulen and A. Fahlman, Phys.Rev.A 42), 1350 (1990).

  4. Rotationally resolved photoelectron spectroscopic study of the Jahn-Teller effect in allene

    NASA Astrophysics Data System (ADS)

    Schulenburg, A. M.; Merkt, F.

    2009-01-01

    The pulsed-field-ionization zero-kinetic-energy photoelectron spectra of allene (C3H4) and perdeuterated allene have been recorded from the first adiabatic ionization energy up to 2200 cm-1 of internal energy in the cations at a resolution sufficient to observe the full rotational structure. The intensity distributions in the spectra are dominated by vibrational progressions in the torsional mode, which were analyzed in the realm of a two-dimensional model of the E ⊗(b1⊕b2) Jahn-Teller effect in the allene cation [C. Woywod and W. Domcke, Chem. Phys. 162, 349 (1992)]. Whereas the rotational structure of the transitions to the lowest torsional levels (00 and 41) are regular and can be qualitatively analyzed in terms of a simple orbital ionization model, the rotational structure of the spectra of the 42 and 43 levels are strongly perturbed. The photoelectron spectrum of C3H4 also reveals several weak vibrational bands in the immediate vicinity of these levels that are indicative of (ro)vibronic perturbations. A slight broadening of the transitions to the 41 levels compared to that of the vibronic ground state and the increase of the number of sharp features in the rotational structure of the spectrum of the 42 level point at the importance of large-amplitude motions not considered in previous treatments of the Jahn-Teller effect in the allene cation.

  5. Storm Spectra

    NASA Technical Reports Server (NTRS)

    2007-01-01

    portion is defined by the day/night boundary (known as the terminator).

    These two images illustrate only a small fraction of the information contained in a single LEISA scan, highlighting just one aspect of the power of infrared spectra for atmospheric studies.

  6. Pu electronic structure and photoelectron spectroscopy

    SciTech Connect

    Joyce, John J; Durakiewicz, Tomasz; Graham, Kevin S; Bauer, Eric D; Moore, David P; Mitchell, Jeremy N; Kennison, John A; Martin, Richard L; Roy, Lindsay E; Scuseria, G. E.

    2010-01-01

    The electronic structure of PuCoGa{sub 5}, Pu metal, and PuO{sub 2} is explored using photoelectron spectroscopy. Ground state electronic properties are inferred from temperature dependent photoemission near the Fermi energy for Pu metal. Angle-resolved photoemission details the energy vs. crystaJ momentum landscape near the Fermi energy for PuCoGa{sub 5} which shows significant dispersion in the quasiparticle peak near the Fermi energy. For the Mott insulators AnO{sub 2}(An = U, Pu) the photoemission results are compared against hybrid functional calculations and the model prediction of a cross over from ionic to covalent bonding is found to be reasonable.

  7. The influence of surface structure on H4SiO4 oligomerization on rutile and amorphous TiO2 surfaces: an ATR-IR and synchrotron XPS study.

    PubMed

    Song, Yantao; Swedlund, Peter J; McIntosh, Grant J; Cowie, Bruce C C; Waterhouse, Geoffrey I N; Metson, James B

    2012-12-11

    Silicic acid (H(4)SiO(4)) is ubiquitous in natural aquatic systems. Applications of TiO(2) in these systems will be influenced by H(4)SiO(4) sorption and oligomerization reactions on the TiO(2) surface, and this can affect many aspects of TiO(2) reactivity. The spatial arrangement of sorption sites on a metal oxide surface can promote specific lateral interactions, such as oligomerization, between sorbed species. In this work we explore the relationship between surface structure and interfacial H(4)SiO(4) oligomerization by quantifying the extent of H(4)SiO(4) sorption and oligomerization on three TiO(2) phases; a rutile phase having well-developed (110) faces (R180), a rutile phase with poorly developed (110) faces (R60), and an amorphous TiO(2) (TiO(2(am))). The in situ ATR-IR spectra measured over time as 0.2 mM H(4)SiO(4) reacted with TiO(2) were quite different on the three TiO(2) phases. The percentage of the surface H(4)SiO(4) that was present as oligomers increased over time on all phases, but after 20 h almost all H(4)SiO(4) on the R180 surface was oligomeric, while the H(4)SiO(4) on TiO(2(am)) was predominantly monomeric. The extent of H(4)SiO(4) oligomerization on R60 was intermediate. When the TiO(2) phases reacted with 1.5 mM H(4)SiO(4) the ATR-IR spectra showed oligomeric silicates dominating the surface of all three TiO(2) phases; however, after 20 h the percentage of the surface H(4)SiO(4) present as three-dimensional polymers was ∼30, 10, and 0% on R180, R60, and TiO(2(am)) respectively. The Si 2s photoelectron peak binding energy (BE) and the H(4)SiO(4) surface coverage (Γ(Si)) were measured by XPS over a range of Γ(Si). For any given Γ(Si) the Si 2s BE's were in the order R180 > R60 > TiO(2(am)). A higher Si 2s BE indicates a greater degree of silicate polymerization. The ATR-IR and XPS results support the existing model for interfacial H(4)SiO(4) oligomerization where linear trimeric silicates are formed by insertion of a solution H(4)SiO(4

  8. Ennoblement of stainless steel studied by x-ray photoelectron spectroscopy

    SciTech Connect

    Olesen, B.H. |; Avci, R.; Lewandowski, Z.

    1998-12-31

    Manganese oxides deposited by biofilms of Leptothrix discophora SP-6 on 316L stainless steel corrosion coupons increased the open circuit potential of the steel to values of +375 mV{sub SCE}. XPS spectra of the deposits compared to spectra of different manganese containing minerals indicated that the deposits were composed of MnO{sub 2}. The redox reaction responsible for the potential change results in electron transfer from the metal substratum to the mineral deposit. To study the processes of manganese dioxide reduction, MnO{sub 2} which had been electroplated on stainless steel was reduced electrochemically. The surface chemistry before and after reduction was analyzed by XPS. The authors demonstrated that the manganese dioxide deposited on stainless steel coupons can be reduced to Mn{sup 2+} by accepting two electrons from the metal. MnOOH was identified as an unstable intermediate product in this reaction. Consequently they hypothesize, that manganese dioxide microbially deposited on stainless steel surfaces can provide an efficient cathodic reaction and accelerate microbially influenced corrosion processes.

  9. Room-temperature oxidation of a GaAs(001) surface induced by the interaction of hyperthermal atomic oxygen and studied by x-ray photoelectron spectroscopy and ion scattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Wolan, John T.; Mount, Charles K.; Hoflund, Gar B.

    1998-03-01

    In this study a hyperthermal oxygen atom source has been used to form an oxide layer on an Ar+-sputtered GaAs(001) surface at room temperature, and this layer has been examined using x-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS). XPS data indicate that the Ga in the near-surface region is oxidized predominantly to Ga2O3 with a significant contribution from GaAsO4 while the As is oxidized predominantly to an AsOx species with significant contributions from As2O3 and GaAsO4 and/or As2O5. The oxide layer thickness is estimated to be about 25 Å, and the XPS Ga:As atom ratio increases from 1.1 to 1.6 during the oxidation. The ISS data indicate that the resulting oxide layer formed is more electrically insulating than a native oxide layer on this surface.

  10. Photoelectron Spectroscopy of Rare-Gas Solvated Nucleobase Anions

    NASA Astrophysics Data System (ADS)

    Buonaugurio, Angela M.; Chen, Jing; Bowen, Kit H.

    2012-06-01

    Gas-phase polar molecular anions [uracil (U^-), thymine (T^-), 1-3 dimethyluracil (DMU^-)] solvated by rare gas atoms were studied by means of negative ion photoelectron spectroscopy. The photoelectron spectrum (PES) of U^-, T^-, and DMU^- each exhibit a distinctive dipole-bound (DB) spectral signature. The spectra of U^-, U^- (Ar)_1,2 and U^- (Kr)_1 also only displayed the DB anion feature. Upon the solvation of more rare gas atoms, the spectra of U^- (Ar)_3, U^- (Kr)_2, and U^- (Xe)1-3 not only retained the DB signature but also exhibited the valence anion features. Moreover, the DB and the valence features shifted together to higher electron binding energies (EBEs) with increasing numbers of rare gas solvent atoms. Therefore, the co-existing DB and the valence anions appeared to be strongly coupled with each other, i.e. they effectively form a single state that is a superposition of both DB and valence anion states. For both U^- and T^- series, the ``onset size" of the Xe, Kr, and Ar solvents for the co-existing of the two anionic states was 1, 2, and 3 respectively. In addition, a minimum of 2 methane (CH_4) molecules or 1 ethane (C_2H_6) molecule were required to induce the coupling between the two states in the T^- series. Thus, the nucleobase anion interaction with non-polar solvent atoms tracks as the sum of the solvent polarizabilities. However for the DMU- series, the DB and the valence anions of DMU^-(Xe)_1, DMU^-(Kr)_2, and DMU^-(Ar)_3 were completely absent in both the mass spectra and the PES. Beyond these ``holes", their PES displayed the similar behaviors to the U^- and T^- series. Extrapolated EA values for these missing species were at or very close to zero, which may explain why they were not seen. However, why this was the case is not clear. With better Franck-Condon overlap between the origins of the NB^- (Rg)_n valence anion and the neutral NB(Rg)n than between those of the NB^- (H2O)n valence anion and the neutral NB(H2O)n, extrapolation of

  11. Scanned-energy mode photoelectron diffraction measurements at beamline 7.0.1

    SciTech Connect

    Toomes, R.; Booth, N.A.; Woodruff, D.P.

    1997-04-01

    This report covers the results of the authors first experimental run, in May 1996, conducted to explore the advantages offered by the high spectral resolution available at the SpectroMicroscopy Facility on beam line 7.0 to conduct scanned-energy mode photoelectron diffraction (PhD). This technique is now a well-established method for the determination of local structure of atomic and molecular adsorbates on well-characterised surfaces. The directly-emitted component of an adsorbate core-level photoelectron wavefield interferes coherently with components of the same wavefield elastically scattered by surrounding atoms, leading to a modulation in the photoemission intensity as a function of kinetic energy in any specific emission direction. A series of such PhD modulation spectra, each typically covering energies from 50-500 eV, for a series of different emission directions, provides the basis for a quantitative structure determination of the emitter-scatterer geometry. Within the last years the authors have developed an integrated approach to extract the structural information from these photoelectron diffraction (PhD) spectra in a quantitative way. A direct data inversion technique (the so-called Projection method) provides a first-order estimate of the local adsorbate geometry in the form of an `image` of the scatterer atoms which are nearest neighbours to the emitter. This information is then used as a starting model for optimisation of the structural parameters by comparing the experimental PhD spectra with the results of multiple scattering simulations using a code developed by Fritzsche. The optimisation uses an automated trial-and-error procedure by minimising a reliability factor which provides an objective measure of the quality of agreement between experiment and theory. The authors have successfully applied this approach to the structure determination of about 30 adsorption systems.

  12. Observation of Strong Resonant Behavior in the Inverse Photoelectron Spectroscopy of Ce Oxide

    SciTech Connect

    Tobin, J G; Yu, S W; Chung, B W; Waddill, G D; Damian, E; Duda, L; Nordgren, J

    2009-12-15

    X-ray Emission Spectroscopy (XES) and Resonant Inverse Photoelectron Spectroscopy (RIPES) have been used to investigate the photon emission associated with the Ce3d5/2 and Ce3d3/2 thresholds. Strong resonant behavior has been observed in the RIPES of Ce Oxide near the 5/2 and 3/2 edges. Inverse Photoelectron Spectroscopy (IPES) and its high energy variant, Bremstrahlung Isochromat Spectroscopy (BIS), are powerful techniques that permit a direct interrogation of the low-lying unoccupied electronic structure of a variety of materials. Despite being handicapped by counting rates that are approximately four orders of magnitude less that the corresponding electron spectroscopies (Photoelectron Spectroscopy, PES, and X-ray Photoelectron Spectroscopy, XPS) both IPES and BIS have a long history of important contributions. Over time, an additional variant of this technique has appeared, where the kinetic energy (KE) of the incoming electron and photon energy (hv) of the emitted electron are roughly the same magnitude as the binding energy of a core level of the material in question. Under these circumstances and in analogy to Resonant Photoelectron Spectroscopy, a cross section resonance can occur, giving rise to Resonant Inverse Photoelectron Spectroscopy or RIPES. Here, we report the observation of RIPES in an f electron system, specifically the at the 3d{sub 5/2} and 3d{sub 3/2} thresholds of Ce Oxide. The resonant behavior of the Ce4f structure at the 3d thresholds has been addressed before, including studies of the utilization of the technique as a probe of electron correlation in a variety of Ce compounds. Interestingly, the first RIPES work on rare earths dates back to 1974, although under conditions which left the state of the surface and near surface regions undefined. Although they did not use the more modern terminology of 'RIPES,' it is clear that RIPES was actually first performed in 1974 by Liefeld, Burr and Chamberlain on both La and Ce based materials. In

  13. Structure, Mobility, and Composition of Transition Metal Catalyst Surfaces. High-Pressure Scanning Tunneling Microscopy and Ambient-Pressure X-ray Photoelectron Spectroscopy Studies

    SciTech Connect

    Zhu, Zhongwei

    2013-12-06

    Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

  14. X-Ray photoelectron spectroscopy study of radiofrequency-sputtered titanium, carbide, molybdenum carbide, and titanium boride coatings and their friction properties

    NASA Technical Reports Server (NTRS)

    Brainard, W. A.; Wheeler, D. R.

    1977-01-01

    Radiofrequency sputtered coatings of titanium carbide, molybdenum carbide and titanium boride were tested as wear resistant coatings on stainless steel in a pin on disk apparatus. X-ray photoelectron spectroscopy (XPS) was used to analyze the sputtered films with regard to both bulk and interface composition in order to obtain maximum film performance. Significant improvements in friction behavior were obtained when properly biased films were deposited on deliberately preoxidized substrates. XPS depth profile data showed thick graded interfaces for bias deposited films even when adherence was poor. The addition of 10 percent hydrogen to the sputtering gas produced coatings with thin poorly adherent interfaces. Results suggest that some of the common practices in the field of sputtering may be detrimental to achieving maximum adherence and optimum composition for these refractory compounds.

  15. Carbon reaction and diffusion on Ni(111), Ni(100), and Fe(110): Kinetic parameters from x-ray photoelectron spectroscopy and density functional theory analysis

    SciTech Connect

    Wiltner, A.; Linsmeier, Ch.; Jacob, T.

    2008-08-28

    This paper investigates the reactivity of elemental carbon films deposited from the vapor phase with Fe and Ni substrates at room temperature. X-ray photoelectron spectroscopy (XPS) measurements are presented as a method for evaluating kinetic reaction data. Carbon films are deposited on different surface orientations representing geometries from a dense atom packing as in fcc (111) to an open surface structure as in fcc (100). During annealing experiments several reactions are observed (carbon subsurface diffusion, carbide formation, carbide decomposition, and graphite ordering). These reactions and the respective kinetic parameters are analyzed and quantified by XPS measurements performed while annealing at elevated temperatures (620-820 K). The resulting activation barriers for carbon subsurface diffusion are compared with calculated values using the density functional theory. The determined kinetic parameters are used to reproduce the thermal behavior of carbon films on nickel surfaces.

  16. Analysis of electronic structure of amorphous InGaZnO/SiO{sub 2} interface by angle-resolved X-ray photoelectron spectroscopy

    SciTech Connect

    Ueoka, Y.; Ishikawa, Y.; Maejima, N.; Matsui, F.; Matsui, H.; Yamazaki, H.; Urakawa, S.; Horita, M.; Daimon, H.; Uraoka, Y.

    2013-10-28

    The electronic structures of amorphous indium gallium zinc oxide (a-IGZO) on a SiO{sub 2} layers before and after annealing were observed by constant final state X-ray photoelectron spectroscopy (CFS-XPS) and X-ray adsorption near-edge structure spectroscopy (XANES). From the results of angle-resolved CFS-XPS, the change in the electronic state was clearly observed in the a-IGZO bulk rather than in the a-IGZO/SiO{sub 2} interface. This suggests that the electronic structures of the a-IGZO bulk strongly affected the thin-film transistor characteristics. The results of XANES indicated an increase in the number of tail states upon atmospheric annealing (AT). We consider that the increase in the number of tail states decreased the channel mobility of AT samples.

  17. X-ray photoelectron spectroscopy characterization of AlGaN surfaces exposed to air and treated in NH4OH solution

    NASA Astrophysics Data System (ADS)

    Hashizume, Tamotsu; Ootomo, Shin-ya; Nakasaki, Ryuusuke; Oyama, Susumu; Kihara, Michio

    2000-05-01

    Chemical properties of Al0.17Ga0.83N surfaces exposed to air and treated in an NH4OH solution were systematically investigated by x-ray photoelectron spectroscopy (XPS). An air-exposed sample showed highly nonstoichiometric surface which included a large amount of Ga and Al oxides. The angle-resolved XPS analysis revealed that the natural oxide layer possessed a complicated composition distribution in depth and that the Al-oxide component was dominant on the topmost layer. A drastic reduction of such Al-oxide component as well as Ga-related oxide was achieved after the treatment in an NH4OH solution at 50 °C for 10 min, resulting in a constant in-depth composition distribution. The NH4OH-based treatment was found to enhance the intensity of the E2 (high) Raman peak and to reduce the root-mean-square value of surface roughness.

  18. Auger electron nanoscale mapping and x-ray photoelectron spectroscopy combined with gas cluster ion beam sputtering to study an organic bulk heterojunction

    SciTech Connect

    Heon Kim, Seong; Heo, Sung; Ihn, Soo-Ghang; Yun, Sungyoung; Hwan Park, Jong; Chung, Yeonji; Lee, Eunha; Park, Gyeongsu; Yun, Dong-Jin

    2014-06-16

    The lateral and vertical distributions of organic p/n bulk heterojunctions for an organic solar cell device are, respectively, investigated using nanometer-scale Auger electron mapping and using X-ray photoelectron spectroscopy (XPS) with Ar gas cluster ion beam (GCIB) sputtering. The concentration of sulfur, present only in the p-type material, is traced to verify the distribution of p-type (donor) and n-type (acceptor) materials in the blended structure. In the vertical direction, a considerable change in atomic sulfur concentration is observed using XPS depth profiling with Ar GCIB sputtering. In addition, Auger electron mapping of sulfur reveals the lateral 2-dimensional distribution of p- and n-type materials. The combination of Auger electron mapping with Ar GCIB sputtering should thereby allow the construction of 3-dimensional distributions of p- and n-type materials in organic photovoltaic cells.

  19. Sn-loss effect in a Sn-implanted a-SiO2 host-matrix after thermal annealing: A combined XPS, PL, and DFT study

    NASA Astrophysics Data System (ADS)

    Zatsepin, D. A.; Zatsepin, A. F.; Boukhvalov, D. W.; Kurmaev, E. Z.; Gavrilov, N. V.

    2016-03-01

    Amorphous a-SiO2 host-matrices were implanted with Sn-ions with and without posterior thermal tempering at 900 °C for 1 h in ambient air. X-ray photoelectron spectroscopy analysis (XPS core-levels, XPS valence band mapping), photoluminescence (PL) probing, and density functional calculations (DFT) were employed to enable a detailed electronic structure characterization of these samples. It was experimentally established that the process of Sn-embedding into the a-SiO2 host occurs following two dissimilar trends: the Sn4+ → Si4+ substitution in a-SiO2:Sn (without tempering), and Sn-metal clustering as interstitials in a-SiO2:Sn (900 °C, 1 h). Both trends were modeled using calculated formation energies and partial densities of states (PDOS) as well as valence band (VB) simulations, which yielded evidence that substitutional defect generation occurs with the help of ion-implantation stimulated translocation of the host-atoms from their stoichiometric positions to the interstitial void. Experimental and theoretical data obtained coincide in terms of the reported Sn-loss effect in a-SiO2:Sn (900 °C, 1 h) due to thermally-induced electronic host-structure re-arraignment, which manifests as backward host-atoms translocation into stoichiometric positions and the posterior formation of Sn-metal clusters.

  20. Self assembling monolayers of dialkynyl bridged Pd(II) thiols obtained by thermally induced multilayer desorption: Thermal and chemical stability investigated by SR-XPS

    NASA Astrophysics Data System (ADS)

    Battocchio, C.; Fratoddi, I.; Bondino, F.; Malvestuto, M.; Russo, M. V.; Polzonetti, G.

    2012-02-01

    Self assembling monolayers (SAMs) of organometallic thiols trans-[HS-Pd(PBu3)2-SH], trans-[HS-Pd(PBu3)2(-Ctbnd C-C6H5)] and trans,trans-[HS-Pd(PBu3)2(-Ctbnd C-C6H4-C6H4-Ctbnd C-Pd(PBu3)2-SH] on gold were obtained from the corresponding multilayers through thermally induced desorption. Temperature-dependent synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS) measurements were carried out on the heated multilayers during the annealing process, in order to investigate the thermal and chemical stability of the systems. SAMs of the same organometallic thiols were also obtained by rinsing the thick films with appropriate solvents. SR-XPS was used to ascertain that the molecular and electronic structure of the two series of SAMs are not influenced by the rinsing or thermal desorption process, i.e. both strategies allow for obtaining well ordered monolayers of organometallic thiols.